AU2020101223A4 - A Method for Preparing Cementitious material with all solid wasteContaining Refining Slag - Google Patents
A Method for Preparing Cementitious material with all solid wasteContaining Refining Slag Download PDFInfo
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/144—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
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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
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00318—Materials characterised by relatively small dimensions, e.g. small thickness
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1037—Cement free compositions, e.g. hydraulically hardening mixtures based on waste materials, not containing cement as such
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
of Descriptions
This invention provides a method for preparing cementitious material with all solid waste
containing refining slag, which belong to the technical field of solid waste resource utilization.
The cementitious materials includes 1%~20% of refining slag, 10%~20% of industrial
by-product gypsum, and the balance is converter steel slag and blast furnace slag. The blast
furnace slag and converter steel slag are ground separately or mixed to a specific surface area of
400~650m2/kg, by mass ratio of 3/4~4/3, and the refining slag and industrial by-product
gypsum are ground separately or mixed to a specific surface area of 300~600m2/kg, the ground
solid slag, refining slag, converter steel slag and industrial by-product gypsum are uniformly
mixed to prepare the cementitious material with all solid waste containing refining slag. This
invention effectively improves the application efficiency of metallurgical slag solid waste,
strengthens the hydration of blast furnace slag in the later period, and significantly reduces the
cost of concrete. At the same time, the synergistic mechanism of converter steel slag and blast
furnace slag promotes the later strength growth of cementitious materials, while refining slag
effectively shortens the initial setting and final setting time of steel slag concrete, and broadens
the application scope of converter steel slag cementitious materials.
Description
Descriptions
A Method for Preparing Cementitious material with all solid wasteContaining Refining Slag
Technical Field This invention relates to the technical field of solid waste resource utilization, in particular to a method for preparing cementitious material with all solid wastecontaining refining slag.
Background Technology Many iron and steel enterprises refer to the slag added in the secondary refining process as refining slag or refining synthetic slag, and some iron and steel enterprises refer to the slag discharged from the secondary refining of molten steel as refining slag, refining slag or casting residue. The refining slag in the present invention refers to the latter, that is, the waste residue after the refining of molten steel.
Refining slag is usually composed of CaO, A1 2 0 3 , SiO 2 and MgO, and its mineralogical phases are olivine (y-C2S),mayenite (C12A7), tricalcium aluminate (C 3A), and a small amount of perovskite (MgO). Refining slag has hydration characteristics, and its main componentC 12A7 is considered to have high hydration characteristics, and it reacts quickly when contacted with water. Moreover, compared with the converter steel slag, the iron oxide content in the refining slag is lower and the alumina content is higher. During the cooling process, the crystal form transition from p-C2S to y-C2S results in a larger volume, making the refining slag almost completely powdered, which is good for grinding.
The main components of converter steel slag are CaO, SiO 2 , A1 2 0 3 , Fe203,MgO and a small amount of MnO, FeO. The main mineral composition of converter steel slag is dicalcium silicate, tricalcium silicate, RO phase and a small amount of free calcium oxide (f-CaO), tetracalcium iron aluminate, which makes it have potential gelling activity. But compared with ordinary Portland cement, the activityof C2S andC3S inconverter steel slag is low and the reaction rate is slow. Therefore, the initial setting and final setting time of the converter steel slag cementitious material is long, the maintenance cost is high, the early strength is low, the concrete has the disadvantages of low dosage and poor workability, and limits the application area of the converter steel slag.
Among the existing technologies, CN101549977 discloses a composite cementitious material and its production method, which includes portland cement, fly ash, steel slag powder, granulated blast furnace slag, pozzolanic mixed material, silica fume, sulfate activator, Alkaline activator, admixture, etc .; the required powder can be obtained through mixing, stirring and other processes. This kind of cementitious material is prepared from a variety of industrial solid wastes, but the cement content is high and the preparation cost is high.
CN105859229A discloses a cement-free green mortar with steel slag as a cementitious material and fine aggregate and its preparation method. This cementitious material has a high content of steel slag, excellent impermeability and sulfate resistance, and high strength. However, this kind of cementitious material uses a lot of admixtures including water reducing agent, dispersing agent, retarder and defoaming agent, which is not in line with the concept of green environmental protection and the preparation cost is also high.
CN108863264A discloses a cementitious material for construction and a preparation method. The amount of steel slag used for this cementitious material increases, and the amount of blast furnace slag decreases, but about 10% of the redispersed latex powder, activator, and additives are added, which significantly increases the preparation cost of this cementitious material and reduces the market value of concrete, and makes it difficult to consume steel slag in large quantities.
CN107056099A discloses a method for preparing low-strength cementitious materials. The preparation method of the cement material is simple in process, and has the characteristics of low energy consumption, high waste slag content and low production cost. However, this kind of cementitious material has the disadvantages of low strength, poor working performance and small application range.
Invention Summary The large proportion of converter steel slag cementitious materials existing in the existing technologies has a slow early hydration rate, the initial and final setting time is too long, and the early strength is low; the utilization rate of metallurgical slag such as converter steel slag and refining slag is large and the utilization rate is low, and a large number of stockpiles have caused a waste of resources and environmental pollution; the potential gelling activity of blast furnace slag has not been fully applied; the potential hydraulic gelling properties of refining slag have not been reasonably utilized, and at the same time, the refining slag hardly participates in the problems of later strength growth. There is no precedent for refining slag to adjust early strength. The present invention provides a method for preparing the cementitious material with all solid waste containing refining slag to solve the above problems.
1. The cementitious material is based on mass percentage, it includes 1%~20% of refining slag, 10%~20% of industrial by-product gypsum, and the balance is converter steel slag and blast furnace slag, and it does not contain cement or cement clinker. Among them, the mass ratio of converter steel slag to blast furnace slag is 3/4~4/3, the specific surface area of refining slag and industrial by-product gypsum is 300m 2/kg~600m2/kg, and the specific surface area of blast furnace slag and converter steel slag is 400m 2 /kg~650m 2/kg.
Among them, the industrial by-product gypsum is one or more of desulfurization gypsum, phosphogypsum, fluorogypsum, lemon gypsum, waste ceramic mould gypsum, titanium gypsum, mirabilite gypsum and salt gypsum.
The converter steel slag is converter steel slag in accordance with YB / T 022 "Steel Slag Used in Cement", in which the content of metal iron is less than 0.5% and the content of free calcium oxide is less than 3%.
The slag is granulated blast furnace slag that complies with GB / T 203 "GranulatedBlast FurnaceSlag Used in Cement".
The method for preparing the cementitious material with all solid wasteis as follows:
First of all, the refining slag, the industrial by-product gypsum, the converter steel slag and the blast furnace slag are batched according to the mass ratio; then, the converter steel slag and blast furnace slag are separately ground to a specific surface area of 400~650m 2 /kg, and the refining slag and industrial by-product gypsum are separately ground to a specific surface area of 300~600m 2 /kg. Finally, the ground solid slag, refining slag, converter steel slag and industrial by-product gypsum are mixed to prepare a cementitious material with all solid wastecontaining refining slag.
Among them, the converter steel slag and blast furnace slag can be mixed and then pulverized to a specific surface area of 400~650m 2/kg.
The refining slag and industrial by-product gypsum can be mixed and then pulverized to a specific surface area of 300~600m 2/kg.
The converter steel slag referred to in the present invention refers to converter slag, electric furnace oxidation slag, etc., excluding metallurgical slag of refining slag. The main components of converter steel slag are CaO, SiO 2 , A1 2 0 3 , Fe203, MgO and a small amount of MnO, FeO. The main mineral composition of converter steel slag is dicalcium silicate, tricalcium silicate, RO phase and a small amount of free calcium oxide(f-CaO), tetracalcium iron aluminate, which makes it have potential gelling activity.
In the full solid waste cementitious system containing refining slag of the present invention, the converter steel slag is ultrafinely ground to fully expose the free calcium oxide, and the hydroxide generated by the reaction with water can promote the continuous hydration of slag to form CSH Gum and MSH gel, so as to provide strength support for the system, at the same time, it solve the problem of poor stability of converter steel slag. The industrial by-product gypsum provides sulfate ions, stimulates converter steel slag, blast furnace slag, refining slag, and provides calcium ions. By using the characteristics of high early hydration rate of refining slag, the shortcomings of long initial setting time and low early strength of converter steel slag-slag-gypsum cementitious material system are solved. To a certain extent, the proportion of converter steel slag in the system is increased, which helps to improve the utilization rate of converter steel slag.
The addition of refining slag in the present invention significantly improves the early hydration rate of this cementitious material system, the initial setting and final setting time of the cementitious material are also significantly shortened, the early strength is significantly improved, and the working performance is significantly improved. The improvement effect of refining slag on the working performance of cementitious materials has increased the quality ratio of converter steel slag to blast furnace slag from the range of 1/4 ~ 1/3 in the published experimental data to the range of 3/4 ~ 4/3, which greatly improves the utilization efficiency of converter steel slag. At present, China's slag has been well utilized, but the comprehensive utilization rate of converter steel slag is very low. The large accumulation of converter steel slag will pollute the environment and bring a serious burden to the country and enterprises. The large proportion of converter steel slag used in the cementitious material of the present invention can provide more divalent cations and higher hydroxide ion concentration for the system. This high alkalinity environment can promote the continuous hydration of the slag and the reaction of generating double salts in order to ensure the continuous growth of the strength of the system. And
The beneficial effects of the above technical solutions of the present invention are as follows:
The above scheme breaks through the ratio of converter steel slag and blast furnace slag in the prior art, and it uses a large proportion of converter steel slag to promote the continuous hydration of the slag in the middle and later stages, so as to improve the double salt effect and maintain the continuous growth of the strength in the later stage; It also improves the problems of the early hydration rate of the converter steel slag cementitious material, the slow initial hydration rate, the long initial and final setting time, and the low early strength by using the characteristics of highly hydrated refining slag and rapid reaction when contacted with water. It provides a new idea for the utilization of metallurgical slag. In the present invention, a large amount of converter steel slag is used for the production of cementitious materials, which has a broad market prospect and a large amount after commissioning, which can greatly accelerate the process of converter steel slag resource utilization and improve the resource shortage and environmental pollution problems facing the country. The specific advantages are as follows:
(1) This kind of cementitious material with all solid wastecontaining refining slag can coordinately dispose of various industrial solid wastes such as blast furnace slag, converter steel slag, refining slag, industrial by-product gypsum, etc. to achieve resource utilization, reduce the cost of cementitious materials, and protect surroundings;
(2) Compared with other steel slag concrete, the content of converter steel slag in the present invention is significantly improved, and the problems of slow hydration rate, long initial and final setting time and low early strength of large proportion of converter steel slag cementitious materials are solved, the scope of its application has been broadened;
(3) This invention improves the early hydration rate of cementitious material by using refining slag, reduces and replaces the use of additives such as accelerator, reduces the cost of cementitious material, and provides new ideas and ways for the utilization of metallurgical slag.
Detailed Description of the Presently Preferred Embodiments In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following will describe in detail with reference to specific embodiments.
This invention provides a method for preparing cementitious material with all solid wastecontaining refining slag.
The cementitious material is based on mass percentage, it includes 1%20% of refining slag, 10%~20% of industrial by-product gypsum, and the balance is converter steel slag and blast furnace slag, and it does not contain cement or cement clinker. Among them, the mass ratio of converter steel slag to blast furnace slag is 3/4~4/3, the specific surface area of refining slag and industrial by-product gypsum is 300m 2 /kg~60Om2/kg, and the specific surface area of blast furnace slag and converter steel slag is 400m2 /kg~65m 2 /kg.
The preparation method of the cementitious material is roughly as follows: First, the refining slag, the industrial by-product gypsum, the converter steel slag and the blast furnace slag are batched according to the mass ratio; then, the converter steel slag and blast furnace slag are separately ground to a specific surface area of 400~650m 2 /kg, and the refining slag and industrial by-product gypsum are separately ground to a specific surface area of 300~600m 2/kg. Finally, the ground solid slag, refining slag, converter steel slag and industrial by-product gypsum are mixed to prepare a cementitious material with all solid wastecontaining refining slag.
It will be described below in conjunction with specific embodiments.
Embodiment 1 Preparation of cementitious materials: the raw materials are mixed and prepared according to the following mass percentages, in which the mass ratio of converter steel slag to blast furnace slag is 3/4, 10% of the refining slag, and 10% of the flue gas desulfurized gypsum, among them, the slag is ground to 560m 2 /kg, the converter steel slag is ground to 450m 2/kg, the refining slag is ground to 350m 2 /kg, and the desulfurized gypsum is ground to 400m 2/kg, in order to stabilize the cementitious materials, the test experiment shall be carried out in accordance with the provisions of GB / T 1346-2011 "Cement Standard Consistency Water Consumption, Setting Time, and Stability Inspection Method". According to the above "cementitious material" ratio, prepare a consistent full solid waste cementitious material. After the test of cake method and Rayleigh clip method, the stability is qualified. After the initial setting time and final setting time test, the initial setting time is determined as 154min, the final setting time is 420min.
450g of cementitious material, 1350g of standard sand, 0.35 of water-to-binder ratio, and 0.5% of polycarboxylate water-reducing agent are used to verify the sand experiment.
The mortar test block is matched as shown in the following table: (Unit: g) Cementitious material Blast Flue gas Standard Water Water Converter furnace slag Refining desulfuriz sand reducer steel slag slag ed gypsum 154.3 205.7 45 45 1350 157.5 2.25
The mortar test block fully mixes the ground material according to a certain mass ratio, and then conducts the mortar test block test according to "GB / T17671-1999 Cement mortarstrength test". Put the slurry in a mold with a size of 40mm x 40mm x 160mm under the condition of temperature 20 5 °C and relative humidity is not less than 60%, and then formed after vibration. Place the formed clean mortar and mortar test blocks in a curing box at 20 1 °C, and humidity is higher than 90% for curing. Then, continue to place in a constant temperature and humidity curing box with a curing temperature of 20 °C 2 °C and a relative humidity of not less than 95% to 3d, 7d, 28d and 56d ages to test the flexural and compressive strength of the rubber sand test block, 3d, 7d, 28d and 56d flexural strength can reach 3.5, 4.2, 4.8 and 5.3MPa respectively, compressive strength can reach 18.2, 26.4, 40.5 and 46.7MPa.
Embodiment 2 Preparation of cementitious materials: the raw materials are mixed and prepared according to the following mass percentages, in which the mass ratio of converter steel slag to blast furnace slag is 1/1, 5% of the refining slag, and 15% of the desulfurized gypsum, among them, the slag is ground to 560m 2 /kg, the converter steel slag is ground to 450m 2/kg, the refining slag is ground to 350m 2 /kg, and the desulfurized gypsum is ground to 400m2/kg, in order to stabilize the cementitious materials, the test experiment shall be carried out in accordance with the provisions of GB / T 1346-2011 "Cement Standard Consistency Water Consumption, Setting Time, and Stability Inspection Method". According to the above "cementitious material" ratio, prepare a consistent full solid waste cementitious material. After the test of cake method and Rayleigh clip method, the stability is qualified. After the initial setting time and final setting time test, the initial setting time is determined as 186min, the final setting time is 465min.
450g of cementitious material, 1350g of standard sand, 0.35 of water-to-binder ratio, and 0.5% of polycarboxylate water-reducing agent are used to verify the sand experiment.
The mortar test block is matched as shown in the following table: (Unit: g)
Cementitiousmaterial Standard Water Flue gas Water Converter Blast Refining desulfurized sand reducer steel slag furnace slag slag gypsum
180 180 22.5 67.5 1350 157.5 2.25
The mortar test block fully mixes the ground material according to a certain mass ratio, and then conducts the mortar test block test according to "GB / T17671-1999 Cement mortarstrength test". Put the slurry in a mold with a size of 40mm x 40mm x 160mm under the condition of temperature 20 5 °C and relative humidity is not less than 60%, and then formed after vibration. Place the formed clean mortar and mortar test blocks in a curing box at 20 1 °C, and humidity is higher than 90% for curing. Then, continue to place in a constant temperature and humidity curing box with a curing temperature of 20 °C 2 °C and a relative humidity of not less than 95% to 3d, 7d, 28d and 56d ages to test the flexural and compressive strength of the rubber sand test block, 3d, 7d, 28d and 56d flexural strength can reach 4.4, 5.4, 5.9 and 6.8MPa respectively, compressive strength can reach 22.2, 36.4, 45.7 and 51.5MPa.
Embodiment 3 Preparation of cementitious materials: the raw materials are mixed and prepared according to the following mass percentages, in which the mass ratio of converter steel slag to blast furnace slag is 4/3, 5% of the refining slag, and 15% of the desulfurized gypsum, among them, the slag is ground to 560m 2 /kg, the converter steel slag is ground to 450m 2/kg, the refining slag is ground to 350m 2 /kg, and the desulfurized gypsum is ground to 400m2/kg, in order to stabilize the cementitious materials, the test experiment shall be carried out in accordance with the provisions of GB / T 1346-2011 "Cement Standard Consistency Water Consumption, Setting Time, and Stability Inspection Method". According to the above "cementitious material" ratio, prepare a consistent full solid waste cementitious material. After the test of cake method and Rayleigh clip method, the stability is qualified. After the initial setting time and final setting time test, the initial setting time is determined as 209min, the final setting time is 490min.
450g of cementitious material, 1350g of standard sand, 0.35 of water-to-binder ratio, and 0.5% of polycarboxylate water-reducing agent are used to verify the sand experiment.
The mortar test block is matched as shown in the following table: (Unit: g)
Cementitiousmaterial Standard Water Flue gas Water Converter Blast Refining desulfurized sand reducer steel slag furnace slag slag gypsum 205.7 154.3 22.5 67.5 1350 157.5 2.25
The mortar test block fully mixes the ground material according to a certain mass ratio, and then conducts the mortar test block test according to "GB / T17671-1999 Cement mortarstrength test". Put the slurry in a mold with a size of 40mm x 40mm x 160mm under the condition of temperature 20 5 °C and relative humidity is not less than 60%, and then formed after vibration. Place the formed clean mortar and mortar test blocks in a curing box at 20 1 °C, and humidity is higher than 90% for curing. Then, continue to place in a constant temperature and humidity curing box with a curing temperature of 20 °C 2 °C and a relative humidity of not less than 95% to 3d, 7d, 28d and 56d ages to test the flexural and compressive strength of the rubber sand test block , 3d, 7d, 28d and 56d flexural strength can reach 3.5, 4.1, 4.7 and 5.MPa respectively, compressive strength can reach 17.2, 25.1, 41.4 and 47.6MPa.
Embodiment 4 Preparation of cementitious materials: the raw materials are mixed and prepared according to the following mass percentages, in which the mass ratio of converter steel slag to blast furnace slag is 1/1, 20% of the refining slag, and 20% of the titanium gypsum, among them, the slag is ground to 560m 2 /kg, the converter steel slag is ground to 450m 2/kg, the refining slag is ground to 350m 2 /kg, and the titanium gypsum is ground to 400m 2/kg, in order to stabilize the cementitious materials, the test experiment shall be carried out in accordance with the provisions of GB / T 1346-2011 "Cement Standard Consistency Water Consumption, Setting Time, and Stability Inspection Method". According to the above "cementitious material" ratio, prepare a consistent full solid waste cementitious material. After the test of cake method and Rayleigh clip method, the stability is qualified. After the initial setting time and final setting time test, the initial setting time is determined as 117min, the final setting time is 355min.
450g of cementitious material, 1350g of standard sand, 0.35 of water-to-binder ratio, and 0.5% of polycarboxylate water-reducing agent are used to verify the sand experiment.
The mortar test block is matched as shown in the following table: (Unit: g)
Cementitiousmaterial Converter Blast Refining Titanium Standard Water Water steel slag furnace slag slag sand reducer gypsum
135 135 90 90 1350 157.5 2.25
The mortar test block fully mixes the ground material according to a certain mass ratio, and then conducts the mortar test block test according to "GB / T17671-1999 Cement mortarstrength test". Put the slurry in a mold with a size of 40mm x 40mm x 160mm under the condition of temperature 20 5 °C and relative humidity is not less than 60%, and then formed after vibration. Place the formed clean mortar and mortar test blocks in a curing box at 20 1 °C, and humidity is higher than 90% for curing. Then, continue to place in a constant temperature and humidity curing box with a curing temperature of 20 °C 2 °C and a relative humidity of not less than 95% to 3d, 7d, 28d and 56d ages to test the flexural and compressive strength of the rubber sand test block , 3d, 7d, 28d and 56d flexural strength can reach 4.8, 5.3, 5.6 and 5.8MPa respectively, compressive strength can reach 20.1, 32.5, 38.7 and 44.2MPa.
Comparative Example 1 Preparation of cementitious materials: the raw materials are mixed and prepared according to the following mass percentages, in which the mass ratio of converter steel slag to blast furnace slag is 8/7, and 15% of the desulfurized gypsum, among them, the slag is ground to 560m 2 /kg, the converter steel slag is ground to 450m 2/kg, and the desulfurized gypsum is ground to 400m 2/kg, in order to stabilize the cementitious materials, the test experiment shall be carried out in accordance with the provisions of GB / T 1346-2011 "Cement Standard Consistency Water Consumption, Setting Time, and Stability Inspection Method". According to the above "cementitious material" ratio, prepare a consistent full solid waste cementitious material. After the test of cake method and Rayleigh clip method, the stability is qualified. After the initial setting time and final setting time test, the initial setting time is determined as 304min, the final setting time is 755min.
450g of cementitious material, 1350g of standard sand, 0.35 of water-to-binder ratio, and 0.5% of polycarboxylate water-reducing agent are used to verify the sand experiment.
The mortar test block is matched as shown in the following table: (Unit: g)
Cementitious material
Converter steel Blast furnace Standard Water slag slag Flue gas Water desulfurized sand reducer
gypsum
204 178.5 67.5 1350 157.5 2.25
The mortar test block fully mixes the ground material according to a certain mass ratio, and then conducts the mortar test block test according to "GB / T17671-1999 Cement mortarstrength test". Put the slurry in a mold with a size of 40mm x 40mm x 160mm under the condition of temperature 20 5 °C and relative humidity is not less than 60%, and then formed after vibration. Place the formed clean mortar and mortar test blocks in a curing box at 20 1 °C, and humidity is higher than 90% for curing. Then, continue to place in a constant temperature and humidity curing box with a curing temperature of 20 °C 2 °C and a relative humidity of not less than 95% to 3d, 7d, 28d and 56d ages to test the flexural and compressive strength of the rubber sand test block , 3d, 7d, 28d and 56d flexural strength can reach 2.8, 3.5, 4.1 and 4.4MPa respectively, compressive strength can reach 13.2, 19.5, 27.4 and 31.9MPa.
Comparative Example 2 Preparation of cementitious materials: the raw materials are mixed and prepared according to the following mass percentages, in which the mass ratio of converter steel slag to blast furnace slag is 5/3, 10% of the refining slag, and 10% of the desulfurized gypsum, among them, the slag is ground to 560m 2 /kg, the converter steel slag is ground to 450m 2/kg, the refining slag is ground to 350m 2 /kg, and the desulfurized gypsum is ground to 400m 2/kg, in order to stabilize the cementitious materials, the test experiment shall be carried out in accordance with the provisions of GB / T 1346-2011 "Cement Standard Consistency Water Consumption, Setting Time, and Stability Inspection Method". According to the above "cementitious material" ratio, prepare a consistent full solid waste cementitious material. After the test of cake method and Rayleigh clip method, the stability is qualified. After the initial setting time and final setting time test, the initial setting time is determined as 420min, the final setting time is 830min.
450g of cementitious material, 1350g of standard sand, 0.35 of water-to-binder ratio, and 0.5% of polycarboxylate water-reducing agent are used to verify the sand experiment.
The mortar test block is matched as shown in the following table: (Unit: g)
Cementitious material
Flue gas Standard Water Converter Blast Refining esulfurized sand reducer steel slag furnace slag slag gypsum
225 135 45 45 1350 157.5 2.25
The mortar test block fully mixes the ground material according to a certain mass ratio, and then conducts the mortar test block test according to "GB / T17671-1999 Cement mortarstrength test". Put the slurry in a mold with a size of 40mm x 40mm x 160mm under the condition of temperature 20 5 °C and relative humidity is not less than 60%, and then formed after vibration. Place the formed clean mortar and mortar test blocks in a curing box at 20 1 °C, and humidity is higher than 90% for curing. Then, continue to place in a constant temperature and humidity curing box with a curing temperature of 20 °C 2 °C and a relative humidity of not less than 95% to 3d, 7d, 28d and 56d ages to test the flexural and compressive strength of the rubber sand test block, 3d, 7d, 28d and 56d flexural strength can reach 1.9, 2.4, 2.8 and 3.2.MPa respectively, compressive strength can reach 9.9, 14.1, 19.5 and 26.3MPa.
Through comparison between Comparative Example 1 and Embodiment 2 and Embodiment 3, it can be seen that the addition of refining slag can significantly shorten the initial setting time of the cementitious material system, the final setting time is slightly shortened, and the strength in the later period is slightly improved. It shows that the addition of refining slag has a significant effect on improving the early working performance of cementitious materials, and is beneficial to improve the later strength.
Through comparison between Comparative Example 2 and Embodiment 1, it can be seen that when the mass ratio of converter steel slag to blast furnace slag is greater than 4/3, due to the increase in the proportion of steel slag, the early workability of the cementitious material decreases and the mortar strength decreases. Although increasing the amount of steel slag can improve environmental and economic benefits, in order to ensure a better use effect, the present invention believes that the quality ratio of converter steel slag to blast furnace slag should not be greater than 4/3.
The above is the preferred embodiment of the present invention. It should be pointed out that for those of ordinary technicians in the technical field, without departing from the principles of the present invention, several improvements and retouches can be made. It should also be regarded as the protection scope of the present invention.
Claims (7)
1. A cementitious material with all solid waste containing refining slag is characterized by a mass percentage, it includes 1%~20% of refining slag, 10%~20% of industrial by-product gypsum, and the balance is converter steel slag and blast furnace slag, and it does not contain cement or cement clinker. Among them, the mass ratio of converter steel slag to blast furnace slag is 3/4~4/3, the specific surface area of refining slag and industrial by-product gypsum is 300m 2/kg~600m 2/kg, and the specific surface area of blast furnace slag and converter steel slag is 400m2 /kg~65Om 2 /kg.
2. A cementitious material with all solid waste containing refined slag according to Claim 1 is characterized in that the industrial by-product gypsum is one or more of flue gas desulfurization gypsum, phosphogypsum, fluorogypsum, lemon gypsum, waste ceramic mould gypsum, titanium gypsum, mirabilite gypsum and salt gypsum.
3. The cementitious material with all solid waste containing refining slag according to Claim 1, characterized in that the converter steel slag is converter steel slag in accordance with YB / T 022 "Steel Slag Used in Cement", in which the content of metal iron is less than 0.5% and the content of free calcium oxide is less than 3%.
4. The cementitious material with all solid waste containing refining slag according to Claim 1, characterized in that the slag is granulated blast furnace slag that complies with GB / T 203 "GranulatedBlast FurnaceSlag Used in Cement".
5. The method for preparing the cementitious material with all solid waste containing refining slag according to Claim 1 is characterized in that, first, the refining slag, the industrial by-product gypsum, the converter steel slag and the blast furnace slag are batched according to the mass ratio; then, the converter steel slag and blast furnace slag are separately ground to a specific surface area of 400~650m 2/kg, and the refining slag and industrial by-product gypsum are separately ground to a specific surface area of 300~600m 2 /kg. Finally, the ground solid slag, refining slag, converter steel slag and industrial by-product gypsum are mixed to prepare a cementitious material with all solid wastecontaining refining slag.
6. The method for preparing the cementitious material with all solid waste containing refining slag according to Claim 5 is characterized in that the converter steel slag and blast furnace slag are mixed and then ground to a specific surface area of 400~650m 2/kg.
7. The method for preparing the cementitious material with all solid waste containing refining slag according to Claim 5 is characterized in that the refining slag and industrial by-product gypsum are mixed and then ground to a specific surface area of 300~600m 2/kg.
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