Method for improving early-stage performance of all-solid waste cementing material

Abstract

The invention relates to a method for improving early-stage performance of an all-solid-waste cementing material, and aims to improve the early-stage performance of the cementing material. At present, the early strength (1d strength) of an all-solid waste cementing material is generally low, but the characteristic is closely related to construction efficiency and is a key limit for large-scale application of the all-solid waste cementing material. Sintering is not included in the working procedures, and the product does not contain cement clinker. The method comprises the following steps: selecting industrial solid wastes such as steel slag, blast furnace water slag, iron alloy slag, silicomanganese slag, industrial byproduct gypsum, sintering fly ash, fly ash, calcined coal gangue and the like as raw materials; the industrial solid waste is subjected to independent or mixed grinding treatment; by optimizing the raw material ratio and introducing key component minerals, the specific surface area of the cementing material is increased, and active sites of the key minerals are dissociated and exposed. The mass of the introduced key components for optimizing the raw material ratio accounts for less than or equal to 15% of the total mass of the cementing material, the mass fraction of the key and active minerals is increased by less than or equal to 10%, and the early strength of the all-solid waste cementing material is increased by 30%.

Description

TECHNICAL FIELD

[0001] The present application relates to the production of full solid waste cementitious materials, and in particular to a method for improving the early performance of full solid waste cementitious materials. BACKGROUND

[0002] In the prior art, the early performance of full solid waste cementitious materials produced from industrial solid waste has not yet reached the optimal effect. Among them, the early performance mainly refers to the 1d compressive strength, and the 3d compressive strength is also generally considered.

[0003] Currently, the main method to improve the early performance of full solid waste cementitious materials is to add early strength agents of organic components such as formate, citrate, phthalic acid, triethanolamine, triisopropanolamine carboxymethyl cellulose, etc. with a small amount of inorganic components. However, the main components of these early strength agents are not effective components in the strength generation process of full solid waste cementitious materials, although they can help to improve the early performance, but the cost is high and cannot eliminate the negative impact on long-term performance, so it has not been widely used.

[0004] For example, Chinese patent CN202411112882.0 discloses an early strength agent for solid waste cementitious material and its preparation method and application. The early strength agent proposed by the patent includes, by weight fraction, 5-10 parts of potassium hydroxide, 3-7 parts of titanium dioxide, 8-12 parts of sodium metaaluminate, 8-12 parts of potassium dihydrogen phosphate, 8-12 parts of sodium citrate and water. Under the cooperation of potassium hydroxide, titanium dioxide, sodium metaaluminate, potassium dihydrogen phosphate and sodium citrate, the addition to the solid waste cementitious material can play a good role in increasing the early strength of the solid waste cementitious material. According to the use requirements, the addition amount of the early strength agent in the solid waste cementitious material can be adjusted to adjust the setting and hardening speed of the solid waste cementitious material.

[0005] Chinese patent CN202411124417.9 discloses an early strength type solid waste cementitious material and its preparation method and application. The solid waste cementitious material proposed by the patent includes, by weight percentage, 4.0-16.6% of power plant slag powder, 64.0-78.7% of slag powder, 12.5-14.7% of sodium silicate, 4.4-5.2% of calcium hydroxide, 0.05-0.1% of triethanolamine and 0.05-0.1% of triisopropanolamine. The invention activates the power plant slag powder and slag powder by using sodium silicate and calcium hydroxide, and the dosage of slag and slag is relatively increased. The material preparation process only needs basic operations such as crushing, grinding, high-pressure atomization and mixing and stirring, and the operation is simple.

[0006] Chinese patent CN202410555032.1 discloses the application of calcium-sodium early strength agent in solid waste-based cementitious materials. The calcium-sodium early strength agent is calcium formate, calcium chloride, sodium sulfate, sodium carbonate or sodium silicate. The solid waste-based cementitious material is prepared from raw materials including steel slag 20-40 parts, slag 20-60 parts, and gypsum 12-20 parts.

[0007] Chinese patent CN202311766897.4 discloses a full-solid waste non-clinker controllable low-strength material and its preparation method. The material uses solid waste materials to replace part of cement as cementitious material, uses iron tailings as aggregate, uses alkali slag and steel slag as alkaline excitation components, and uses desulfurization gypsum as sulfate excitation component. A new type of cementitious material is developed by alkali-sulfate composite excitation of fly ash and mineral powder, which can replace cement, effectively reduce cost, and consume a large amount of solid waste, improving the utilization rate of solid waste. The polycarboxylate superplasticizer is grafted with epoxy resin, effectively improving the high temperature resistance. The early strength agent is added with o-phthalic acid-sorbitol ester, and its graft product can effectively improve the strengthening performance of the early strength agent. Carboxymethyl cellulose is grafted with sodium dodecyl sulfate, and the air entraining and thickening function is greatly improved.

[0008] Another type of early strength agent is inorganic early strength agent produced from minerals. This type of early strength agent is essentially a "precursor mineral" that pre-prepares a hydrated cementitious phase and is added to the cementitious material. This type of early strength agent can improve the early strength of the cementitious material without much impact on long-term performance. However, the production conditions are relatively harsh, the process is complex, the cost is high, and the application is limited to a certain extent.

[0009] For example, Chinese patent CN202310966857.8 discloses a method for preparing a solid waste-based cementitious material special early strength agent using tailings waste. The components include tailings waste extractant 30-40%, reinforcing agent 5-30%, silica ash 15-20%, quicklime 5-10%, and Na2CO3 20-25% by mass percentage. The invention extracts Si and Al phases from the tailings waste by adding sodium hydroxide to the ground tailings waste and performing a hydrothermal reaction, then adjusting the pH to precipitate Si and Al phases from the liquid phase, thereby realizing the preparation of tailings waste extractant. The tailings waste extractant and silica ash in the components contain a large amount of active Si and Al phases, which can react with Ca(II) generated by the hydration of steel slag, desulfurization gypsum, etc. to form C-S-H gel and ettringite, which is an important source of early and late strength of cementitious materials, and can improve the early strength of the early strength agent without affecting its late strength. SUMMARY

[0010] In order to solve the technical problems of high cost and decline of long-term compressive and flexural properties in the process of improving early strength performance by early strength agent in the prior art, the application provides a method for improving early and early performance of full solid waste cementitious material.

[0011] The method for improving early and early performance of full solid waste cementitious material does not include sintering in the production process of the full solid waste cementitious material, and does not include cement clinker in the cementitious material product, and the method for improving early and early performance of full solid waste cementitious material comprises the following steps:

[0012] S1, raw material crushing and screening: selecting industrial solid waste as the raw material of the full solid waste cementitious material, crushing the industrial solid waste through a crushing device, and then screening to obtain fine particles of the industrial solid waste;

[0013] S2, fine grinding treatment: the fine particles of the industrial solid waste in S1 are subjected to fine grinding treatment to obtain the industrial solid waste powder;

[0014] S3, powder activation treatment: the industrial solid waste powder in S2 is subjected to physical activation in whole or in part, but not for the purpose of improving the specific surface area;

[0015] S4, key active mineral addition: adding key active minerals to the activated industrial solid waste powder in S3 to prepare a cementitious material;

[0016] S5, standard paste test block preparation: preparing the cementitious material in S4 into a standard paste test block;

[0017] S6, performance inspection: inspecting the early and early performance of the full solid waste cementitious material with time change for the standard paste test block in S5, and adjusting the process parameters of the foregoing steps to obtain the process parameter selection of the full solid waste cementitious material corresponding to the best early and early performance parameters.

[0018] Optionally, the industrial solid waste in S1 is at least two of steel slag, blast furnace slag, ferroalloy slag, silicon-manganese slag, industrial by-product gypsum, sintering dust removal ash, fly ash and calcined coal gangue, and the mass of the industrial solid waste accounts for more than 30% of the total mass of the cementitious material.

[0019] Optionally, the particle size of the fine particles of the industrial solid waste in S1 is-0.35mm to-1mm.

[0020] Optionally, the specific surface area of the industrial solid waste powder in S2 is greater than 350m 2 / kg.

[0021] Optionally, the specific surface area of the industrial solid waste powder in S2 is 450-550m 2 / kg.

[0022] Optionally, S3 physical activation is achieved by improving the degree of dissociation and exposure of active sites of key mineral components, and optimizing the raw material ratio and introducing key mineral components to optimize the process performance of cementitious materials.

[0023] Optionally, the total specific surface area of the single finely ground industrial solid waste in S3 powder activation treatment is increased by 35-50% compared with the powder described in S1, which is more economical and technical.

[0024] Optionally, in S3 powder activation treatment, the dissociation degree of calcium-containing minerals, silicate minerals, sulfate minerals and other key active minerals is increased by 40-45% after mixing and semi-milling of industrial solid waste, and the intergrowth rate with calcium ferrite and magnesium ferrite minerals is 5-40%.

[0025] Optionally, the exposure of active sites of key minerals is achieved by increasing the specific surface area of cementitious materials and dissociating and exposing the active sites of key minerals.

[0026] Optionally, the optimization of raw material ratio and the introduction of key components increase the content of key and active minerals without changing the overall mineral composition of the raw material, and the mass fraction of key and active minerals is increased by ≤10%.

[0027] Optionally, the single solid waste fine grinding refers to the fine grinding of industrial solid wastes such as steel slag, blast furnace slag, ferroalloy slag, silicon manganese slag, industrial by-product gypsum, sinter dust, fly ash, calcined coal gangue, etc.

[0028] Optionally, the multi-solid waste mixed semi-milling refers to mixing two or more of industrial solid wastes such as steel slag, blast furnace slag, ferroalloy slag, silicon manganese slag, industrial by-product gypsum, sinter dust, fly ash, calcined coal gangue, etc.

[0029] Optionally, the stirring and mixing are achieved by mechanical, gas, gravity or centrifugal force.

[0030] Optionally, the method for improving the early performance of the full solid waste cementing material according to claim 5, wherein the 1d compressive strength of the standard net paste test block is improved by more than 100%, the 1d final compressive strength is more than 32 MPa, the 1d flexural strength is improved by more than 100%, and the 1d final flexural strength is more than 18 MPa, and most of them are more than 21 MPa; the 3d compressive strength is improved by more than 100%, the 3d final compressive strength is more than 45 MPa, the 3d flexural strength is improved by more than 100%, and the 3d final flexural strength is more than 29 MPa; the 28d compressive strength is improved by more than 100%, the 28d final compressive strength is more than 90 MPa, and the highest is more than 100 MPa, the 28d flexural strength is improved by more than 100%, and the 28d final flexural strength is more than 35 MPa, and most of them are more than 50 MPa; the pH value of the cementing material is 12.0-12.3, and the manufacturing cost of the cementing material is 30-80 yuan / ton.

[0031] Technical principle of the present inventors:

[0032] The early performance of the cementing material is improved by optimizing the treatment and activation process of the industrial solid waste. The production process of the full solid waste cementing material does not include sintering, and the product does not contain cement clinker. First, the total specific surface area of the full solid waste cementing material is improved by fine grinding, and the hydration cementing activity is preliminarily improved. Then, through physical activation, including optimizing the raw material ratio and introducing key component minerals. The hardness difference of the minerals in the industrial solid waste is used in the form of "self-milling" to improve the total specific surface area, at the same time, the active sites in the key minerals are exposed and dissociated, and the hydration cementing activity is improved by improving the specific surface area of the key active minerals. At the same time, the intergrowth rate of the key calcium-containing minerals, silicate minerals, sulfate minerals and calcium ferrite, magnesium ferrite minerals is reduced, and the steric effect of the two inert ferrite minerals in the early hydration is eliminated, and the early performance of the full solid waste cementing material is improved. Finally, the purpose of optimizing the raw material ratio and introducing key components is to improve the total content of calcium-containing minerals, silicate minerals and sulfate minerals in the raw materials, and improve the early hydration strength.

[0033] Compared with the prior art, the above technical scheme has at least the following beneficial effects:

[0034] The above scheme is mainly to improve the early performance of the full solid waste cementitious material by enhancing the dissociation degree of the key mineral components, and is realized by the mixed semi-autogenous grinding. The mixed semi-autogenous grinding is generally considered to be unsuitable for dry fine grinding, and has never been studied and used in the production of full solid waste cementitious material or even cement, because of the extremely low grinding efficiency and almost no contribution to the mechanical properties of the full solid waste cementitious material. However, through the systematic research of the team of Beijing University of Science and Technology, it has been proved that the mixed semi-autogenous grinding can produce a small amount of high-activity mineral powder, and significantly improve the early performance of the full solid waste cementitious material. Based on the research results, the application proposes to first improve the specific surface area and overall activity of the industrial solid waste by fine grinding, and then improve the dissociation degree and early hydration and cementation activity of the key mineral components by mixed semi-autogenous grinding process, so as to obtain excellent mechanical properties at all ages (including early age).

[0035] In special cases, the components introduced in the application are also in mineral form, and are all existing components in the full solid waste cementitious material. These mineral components can all form a cementation phase in the early stage of the hydration and cementation process, and will not affect the long-term mechanical properties. BRIEF DESCRIPTION OF DRAWINGS

[0036] In order to more clearly illustrate the technical solutions in the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments description. Obviously, the drawings in the following description only some embodiments of the application, and for those skilled in the art, other drawings can also be obtained without creative labor.

[0037] Figure 1 is a process flow diagram of a method for improving the early performance of the full solid waste cementitious material according to the embodiment 1 of the application. DETAILED DESCRIPTION

[0038] The technical solutions in the application will be described below with reference to the drawings.

[0039] In the embodiments of the application, the words such as "example", "for example" are used to represent as an example, illustration or description. Any embodiment or design scheme described as "example" in the application should not be interpreted as more preferred or more advantageous than other embodiments or design schemes. In fact, the word "example" is intended to present the concept in a specific way. In addition, in the embodiments of the application, the meaning expressed by "and / or" can be both, or can be one of the two.

[0040] In the embodiments of the application, "image" and "picture" can be used interchangeably sometimes. It should be pointed out that when the distinction is not emphasized, the meanings expressed are consistent.

[0041] In the embodiments of the present application, sometimes the subscript such as W1 may be written in the form of non-subscript such as W1, and when the difference is not emphasized, the meanings expressed are consistent.

[0042] To make the technical problems, technical solutions and advantages to be solved by the present application clearer, specific embodiments will be described in detail below with reference to the drawings.

[0043] A method for improving the early performance of a full-solid waste cementitious material, the production process of the full-solid waste cementitious material does not include sintering, and the cementitious material product does not include cement clinker, the method for improving the early performance of the full-solid waste cementitious material comprises the following steps:

[0044] S1, raw material crushing and screening: selecting industrial solid waste as the raw material of the full-solid waste cementitious material, crushing the industrial solid waste through a crushing device, and then screening to obtain fine particles of the industrial solid waste;

[0045] S2, fine grinding treatment: fine grinding the fine particles of the industrial solid waste in S1 to obtain the industrial solid waste powder;

[0046] S3, powder activation treatment: physically activating all or part of the industrial solid waste powder in S2, but not aiming to improve the specific surface area;

[0047] S4, key active mineral addition: adding key active minerals to the activated industrial solid waste powder in S3 to prepare a cementitious material;

[0048] S5, standard paste test block preparation: preparing the cementitious material in S4 into a standard paste test block;

[0049] S6, performance inspection: inspecting the early performance of the full-solid waste cementitious material over time for the standard paste test block in S5, and adjusting the process parameters of the foregoing steps to obtain the process parameters of the full-solid waste cementitious material corresponding to the optimal early performance parameters.

[0050] In particular, the industrial solid waste in S1 is at least two of steel slag, blast furnace slag, ferroalloy slag, silicon-manganese slag, industrial by-product gypsum, sintering dust removal ash, fly ash and calcined coal gangue, and the mass of the industrial solid waste accounts for more than 30% of the total mass of the cementitious material.

[0051] In particular, the fine particles of the industrial solid waste in S1 have a particle size of -0.35mm to -1mm.

[0052] In particular, the industrial solid waste powder in S2 has a specific surface area of >350m 2 / kg.

[0053] In particular, the industrial solid waste powder in S2 has a specific surface area of 450-550m 2 / kg.

[0054] In particular, the S3 physical activation is achieved by improving the dissociation degree and exposure degree of active sites of key mineral components, and optimizing the raw material ratio and introducing key mineral components to optimize the process performance of cementitious materials.

[0055] In particular, the total specific surface area of the single finely ground industrial solid waste in the S3 powder activation treatment is 35-50% higher than that of the powder described in S1, which is more optimal in economic and technical indicators.

[0056] In particular, in the S3 powder activation treatment, the mixed finely ground industrial solid waste, and the mixed semi-autogenous grinding, the dissociation degree of key active minerals such as calcium-containing minerals, silicate minerals, and sulfate minerals is improved by 40-45%, and the intergrowth rate with calcium ferrite and magnesium ferrite minerals is 5-40%.

[0057] In particular, the improvement of the specific surface area of cementitious materials by single solid waste fine grinding and the exposure of key mineral active sites by multi-solid waste mixed semi-autogenous grinding or stirring are used to improve the specific surface area of cementitious materials by single solid waste fine grinding, and to expose the active sites of key minerals by the hardness difference of the constituent minerals in solid waste.

[0058] In particular, the optimization of raw material ratio and the introduction of key components improve the content of key and active minerals without changing the overall mineral composition of the raw materials, and the mass fraction of key and active minerals is improved by ≤10%.

[0059] In particular, the single solid waste fine grinding refers to the fine grinding of industrial solid wastes such as steel slag, blast furnace slag, ferroalloy slag, silicon-manganese slag, industrial by-product gypsum, sintering dust removal ash, fly ash, and calcined coal gangue, and the specific surface area after fine grinding is improved by ≤55% compared to before fine grinding.

[0060] In particular, the multi-solid waste mixed semi-autogenous grinding refers to the mixing of two or more of industrial solid wastes such as steel slag, blast furnace slag, ferroalloy slag, silicon-manganese slag, industrial by-product gypsum, sintering dust removal ash, fly ash, and calcined coal gangue, and the dissociation degree of key active minerals such as calcium-containing minerals, silicate minerals, and sulfate minerals is improved by ≥50% by mixed semi-autogenous grinding, and the intergrowth rate with calcium ferrite and magnesium ferrite minerals is ≤40%.

[0061] In particular, the stirring and mixing are achieved by mechanical, gas, gravitational or centrifugal force.

[0062] In particular, the method for improving the early performance of all-solid waste cementitious materials according to claim 5 is characterized in that the 1d compressive strength of the standard slurry test block is improved by more than 100%, the 1d final compressive strength is greater than 32 MPa, the 1d flexural strength is improved by more than 100%, the 1d final flexural strength all reaches more than 18 MPa, and most of them reach more than 21 MPa; the 3d compressive strength is improved by more than 100%, the 3d final compressive strength all reaches more than 45 MPa, the 3d flexural strength is improved by more than 100%, and the 3d final flexural strength all reaches more than 29 MPa; the 28d compressive strength is improved by more than 100%, the 28d final compressive strength all reaches more than 90 MPa, and the highest exceeds 100 MPa, the 28d flexural strength is improved by more than 100%, the 28d final flexural strength is more than 35 MPa, and most of them are above 50 MPa; the pH value of the cementitious material is 12.0-12.3, and the manufacturing cost of the cementitious material is 30-80 yuan / ton.

[0063] Example 1

[0064] A method for improving the early performance of all-solid waste cementitious materials, wherein the industrial solid waste used is steel slag, ferroalloy slag, and industrial by-product gypsum from a certain place in Liaoning. The method for improving the early performance of all-solid waste cementitious materials is combined with Figure 1 The steps are as follows:

[0065] S1: crushing the above industrial solid waste into fine particles with a particle size range of -0.3mm;

[0066] S2: Grind the fine particles obtained in S1 into a powder with a specific surface area of ​​350m² / kg;

[0067] S3: Finely grind the steel slag alone. After fine grinding, the overall specific surface area is increased by 35% compared with the powder in S1. Then, it is mixed with other industrial solid waste powders using a mixing machine.

[0068] S4: Introducing calcium-containing minerals, the proportion of key active minerals in the total mass of the cementitious material is 5%, and the mass fraction is increased by 2%;

[0069] S5: Use the prepared cementitious material to make a standard slurry test block, with a water consumption of 30wt.%;

[0070] S6: According to the above steps, the 1d compressive strength of the all-solid waste cementitious material is increased from 1.98MPa to 32.31MPa, and the 1d flexural strength is increased from 1.31MPa to 21.96MPa; the 3d compressive strength is increased from 4.29MPa to 45.45MPa, and the 3d flexural strength is 30.67MPa; the 28d compressive strength is 98.26MPa, and the flexural strength is 59.37MPa; the pH value of the cementitious material is 12.0-12.3; the manufacturing cost of the cementitious material is about 30.5 yuan / ton.

[0071] Example 2

[0072] A method for improving the early performance of a full solid waste cementitious material, the industrial solid waste used is steel slag, blast furnace slag, ferroalloy slag, fly ash and calcined coal gangue from a certain place in Inner Mongolia Autonomous Region, the method for improving the early performance of the full solid waste cementitious material combines Figure 1 the following steps:

[0073] S1: crushing the industrial solid waste into fine particles with a particle size range of -5 mm;

[0074] S2: finely grinding the fine particles obtained in S1 into a powder with a specific surface area of 600 m² / kg;

[0075] S3: mixing the finely ground steel slag, blast furnace slag, ferroalloy slag, fly ash and calcined coal gangue, after mixing, the key active mineral monomer dissociation degree of calcium-containing minerals, silicate minerals and sulfate minerals is improved by 50%, and the intergrowth rate with calcium ferrite and magnesium ferrite minerals is 40%;

[0076] S4: introducing silicate minerals and sulfate minerals, the proportion of key active minerals in the total mass of the cementitious material is 15%, and the mass fraction is improved by 10%;

[0077] S5: using the prepared cementitious material to make standard neat paste test blocks, the water content is 30wt.%;

[0078] S6: according to the above steps, the 1d compressive strength of the full solid waste cementitious material is improved from 1.96 MPa to 35.78 MPa, the 1d flexural strength is improved from 1.23 MPa to 18.95 MPa; the 3d compressive strength is improved from 4.29 MPa to 55.49 MPa, the 3d flexural strength is improved from 3.03 MPa to 29.86 MPa; the 28d compressive strength is 90.05 MPa, the flexural strength is 58.34 MPa; the pH value of the cementitious material is 12.0-12.3; the manufacturing cost of the cementitious material is about 21 yuan / ton.

[0079] Example 3

[0080] A method for improving the early performance of a full solid waste cementitious material, the industrial solid waste used is steel slag, industrial by-product gypsum, fly ash, blast furnace slag from a certain place in Hebei Province, the method for improving the early performance of the full solid waste cementitious material combines Figure 1 the following steps:

[0081] S1: crushing the industrial solid waste into fine particles with a particle size range of -0.35 mm to -1 mm;

[0082] S2: finely grinding the fine particles obtained in S1 into a powder with a specific surface area of 450 m² / kg;

[0083] S3: separately finely grinding blast furnace slag and steel slag, after fine grinding, the total specific surface area of the powder is increased by 40% and 38.5% respectively than that of S1, and then mixing with other industrial solid waste powder by gravity stirring;

[0084] S4: introducing calcium-containing minerals and silicate minerals, the proportion of key active minerals in the total mass of cementitious materials is 10%, and the mass fraction is increased by 5%;

[0085] S5: using the prepared cementitious material to make standard neat paste test blocks, the water consumption is 30wt.%;

[0086] S6: according to the above steps, the 1d compressive strength of the full solid waste cementitious material is increased from 1.82MPa to 36.65MPa, and the 1d flexural strength is increased from 1.18MPa to 21.91MPa; the 3d compressive strength is increased from 4.29MPa to 65.62MPa, and the 3d flexural strength is increased from 3.12MPa to 43.87MPa; the 28d compressive strength is 99.19MPa, and the flexural strength is 56.77MPa, which is increased by 11.26% and 7.53% respectively; the pH value of the cementitious material is 12.0-12.3; the manufacturing cost of the cementitious material is about 42 yuan / ton.

[0087] Example 4

[0088] A method for improving the early performance of full solid waste cementitious material, the industrial solid waste used is steel slag, blast furnace slag and industrial by-product gypsum in a certain place in Fujian, and the method for improving the early performance of full solid waste cementitious material combines Figure 1 the following steps:

[0089] S1: crushing the industrial solid waste into fine particles with a particle size range of-0.35mm to-1mm;

[0090] S2: finely grinding the fine particles obtained in S1 into a powder with a specific surface area of 550m² / kg;

[0091] S3: mixing finely ground steel slag, blast furnace slag and industrial by-product gypsum, after mixing semi-autogenous grinding, the key active minerals such as calcium-containing minerals, silicate minerals and sulfate minerals are increased by 45%, and the intergrowth rate with calcium ferrite and magnesium ferrite minerals is 20%;

[0092] S4: introducing sulfate minerals, the proportion of key active minerals in the total mass of cementitious materials is 12%, and the mass fraction is increased by 7%;

[0093] S5: using the prepared cementitious material to make standard neat paste test blocks, the water consumption is 30wt.%;

[0094] S6: The above steps are implemented, and the 1d compressive strength of the full solid waste cementing material is increased from 1.96 MPa to 52.78 MPa, and the 1d flexural strength is increased from 1.41 MPa to 22.07 MPa; the 3d compressive strength is increased from 4.31 MPa to 65.58 MPa, and the 3d flexural strength is increased from 3.17 MPa to 34.06 MPa; the 28d compressive strength is 101.26 MPa, and the flexural strength is 56.29 MPa; the pH value of the cementing material is 12.0-12.3; and the manufacturing cost of the cementing material is about 55 yuan / ton.

[0095] Example 5

[0096] A method for improving the early performance of a full solid waste cementing material, the industrial solid waste used is steel slag, iron alloy slag, industrial by-product gypsum, and sintering dust in a certain place in Guangdong, the method for improving the early performance of the full solid waste cementing material combines Figure 1 the following steps:

[0097] S1: crushing the industrial solid waste to fine particles with a particle size range of -0.35 mm to -1 mm;

[0098] S2: finely grinding the fine particles obtained in S1 into a powder with a specific surface area of 500 m² / kg;

[0099] S3: separately finely grinding the iron alloy slag and the steel slag, and after fine grinding, the total specific surface area is increased by 50% and 46.5% respectively compared with the powder in S1;

[0100] S4: introducing silicate minerals, the proportion of key active minerals in the total mass of the cementing material is 8%, and the mass fraction is increased by 6%;

[0101] S5: using the prepared cementing material to make standard neat paste test blocks, and the water content is 30wt.%;

[0102] S6: The above steps are implemented, and the 1d compressive strength of the full solid waste cementing material is increased from 1.89 MPa to 42.74 MPa, and the flexural strength is 25.71 MPa; the 3d compressive strength is increased from 4.24 MPa to 55.11 MPa, and the 3d flexural strength is increased from 2.97 MPa to 31.95 MPa; the 28d compressive strength is 85.51 MPa, and the flexural strength is 35.26 MPa; the pH value of the cementing material is 12.0-12.3; and the manufacturing cost of the cementing material is about 31 yuan / ton.

[0103] Example 6

[0104] A method for improving the early performance of a full solid waste cementing material, the industrial solid waste used is mixed finely ground steel slag, blast furnace water slag, iron alloy slag and fly ash in a certain place in Shaanxi, the method for improving the early performance of the full solid waste cementing material combines Figure 1 the following steps:

[0105] S1: crushing industrial solid waste into fine particles with a particle size range of -0.35 mm to -1 mm;

[0106] S2: finely grinding the fine particles obtained in S1 into a powder with a specific surface area of 480 m² / kg;

[0107] S3: mixing finely ground steel slag, blast furnace slag, ferroalloy slag and fly ash, after mixing semi-autogenous grinding, the key active mineral monomer dissociation degree of calcium-containing minerals, silicate minerals and sulfate minerals is increased by 42%, and the intergrowth rate with calcium ferrite and magnesium ferrite minerals is 15%;

[0108] S4: introducing calcium-containing minerals and sulfate minerals, the proportion of key active minerals in the total mass of cementitious materials is 9%, and the mass fraction is increased by 4%;

[0109] S5: using the prepared cementitious material to make standard neat paste test blocks, the water consumption is 30 wt.%;

[0110] S6: according to the above steps, the 1d compressive strength of the full solid waste cementitious material is increased from 2.07 MPa to 52.70 MPa, and the 1d flexural strength is increased from 1.35 MPa to 22.03 MPa; the 3d compressive strength is increased from 4.29 MPa to 65.62 MPa, and the 3d flexural strength is increased from 3.25 MPa to 34.08 MPa; the 28d compressive strength is 90.12 MPa, and the flexural strength is 59.61 MPa; the pH value of the cementitious material is 12.0-12.3; the manufacturing cost of the cementitious material is about 31 yuan / ton.

[0111] Comparative Example 1:

[0112] Comparative Example 6, the operation is as follows:

[0113] S1: crushing industrial solid waste into fine particles with a particle size range of -0.2 mm;

[0114] S2: finely grinding the fine particles obtained in S1 into a powder with a specific surface area of 300 m² / kg;

[0115] S3: separately grinding the steel slag, the total specific surface area after grinding is increased by 30% compared with the powder in S1;

[0116] S4: introducing calcium-containing minerals, the proportion of key active minerals in the total mass of cementitious materials is 4%, and the mass fraction is increased by 1%;

[0117] S5: using the prepared cementitious material to make standard neat paste test blocks, the water consumption is 30 wt.%;

[0118] S6: The implementation is carried out according to the above steps, and the 1d compressive strength of the full-solid waste cementing material is increased from 2.07 MPa to 12.16 MPa, and the 1d flexural strength is increased from 1.35 MPa to 5.37 MPa; the 3d compressive strength is increased from 4.29 MPa to 14.63 MPa, and the 3d flexural strength is increased from 3.03 MPa to 5.86 MPa; the 28-day compressive strength is 48.89 MPa, and the flexural strength is 26.58 MPa; the pH value of the cementing material is 12.0-12.5, the process cost is 72% of that of Example 6; and the manufacturing cost of the cementing material is about 16 yuan / ton.

[0119] Comparative Example 2:

[0120] Comparative Example 6, the operation is as follows:

[0121] S1: The industrial solid waste is crushed to fine particles with a particle size range of -6 mm;

[0122] S2: The fine particles obtained in S1 are finely ground into a powder with a specific surface area of 650 m² / kg;

[0123] S3: The fine grinding steel slag, blast furnace slag, ferroalloy slag, fly ash and calcined coal gangue are mixed, and the key active mineral monomer dissociation degree of the mixed semi-autogenous grinding calcium-containing mineral, silicate mineral and sulfate mineral is increased by 60%, and the intergrowth rate with calcium ferrite and magnesium ferrite mineral is 45%;

[0124] S4: Introduce silicate minerals and sulfate minerals, and the proportion of key active minerals in the total mass of cementing material is 16%, and the mass fraction is increased by 12%;

[0125] S5: The prepared cementing material is used to make standard neat paste test blocks, and the water consumption is 30wt.%.

[0126] S6: The implementation is carried out according to the above steps, and the 1d compressive strength of the full-solid waste cementing material is increased from 2.07 MPa to 12.16 MPa, and the 1d flexural strength is increased from 1.35 MPa to 5.37 MPa; the 3d compressive strength is increased from 4.29 MPa to 14.63 MPa, and the 3d flexural strength is increased from 3.03 MPa to 5.86 MPa; the 28-day compressive strength is 48.89 MPa, and the flexural strength is 26.58 MPa; the pH value of the cementing material is 12.0-12.5, the process cost is 72% of that of Example 6; and the manufacturing cost of the cementing material is about 16 yuan / ton.

[0127] Comparative analysis is as follows:

[0128] Comparative Example 1: Due to the data being lower than the lower limit of the preferred range and the fine particle size being finer, the activity of the cementing material is insufficient, and the early performance decreases significantly. At the same time, due to the reduction of grinding time and power consumption, the process cost is reduced by 28%.

[0129] Comparative Example 2: Since the data is higher than the upper limit of the preferred range, and the maximum particle size after crushing reaches 6 mm, although the performance of the full solid waste cementitious material is improved in the early stage, the process cost is also increased by 62%. Compared with Example 6, there is no advantage in performance and processing cost.

[0130] Conclusion: The above comparative examples show that data outside the preferred range will result in little performance or high cost of cementitious material, further verifying the importance of data within the preferred range.

[0131]

[0132] Comparing Comparative Examples 1-3 and Examples 1-3, it is found that the strength, plasticity, toughness, yield ratio, high temperature performance, corrosion performance, etc. of the steel product of the examples of the application all meet the requirements of the application. In Comparative Example 1, the composition does not meet the requirements of the claims, and the precipitation amount does not meet the requirements of the application, so the web room temperature strength and high temperature performance do not meet the requirements. In Comparative Example 2, the second stage rolling is not followed by water cooling, but direct air cooling to 835°C for rolling, which is not easy to cause a large core surface temperature difference, and the deformation of the center part is small during rolling, so the deformation accumulation is small, especially the deformation of the web position is small, and it is not easy to refine the microstructure during the subsequent phase change, and the residence time at high temperature is too long, which will cause grain growth, affecting the strength of the microstructure and performance after phase change. In Comparative Example 3, the flange is not water mist cooled after the second stage rolling, but directly air cooled to room temperature, which is not easy to speed up the cooling speed of the flange, so that more bainite microstructure is obtained, which will cause uneven overall performance, so it does not meet the requirements of the application.

[0133] In summary, the method of the application, compared with other traditional methods, prepares high-strength, anti-seismic, weather-resistant and fire-resistant H-shaped steel with uniform room temperature and high temperature performance through vacuum smelting and casting into blanks, hot rolling and cooling between rolling passes, and multi-stage hot rolling and cooling after rolling. The preparation method is simple, easy to operate, green, low in cost, short in process, high in efficiency, and conducive to large-scale industrial production and promotion.

[0134] It should be understood that the term "and / or" herein merely describes the association relationship of the associated objects, and indicates that there can be three relationships, for example, A and / or B can represent: A exists alone, A and B exist together, and B exists alone, where A and B can be singular or plural. In addition, the character " / " herein generally represents an "or" relationship between the front and rear associated objects, but can also represent an "and / or" relationship, which can be understood in combination with the context before and after.

[0135] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or similar expressions means any combination of the items, including any combination of single item or multiple items. For example, at least one of a, b, or c can mean a, b, c, a-b, a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0136] It should be understood that the order of the above processes does not mean the order of execution in various embodiments of the present application. The order of execution of the processes should be determined by their functions and inherent logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0137] The above is only a specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any person skilled in the art can easily think of changes or replacements within the technical scope disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for improving early age performance of a full solid waste cementitious material, characterized by, The production process of the full solid waste cementitious material does not include sintering, and the cementitious material product does not include cement clinker, and the method for improving the early performance of the full solid waste cementitious material comprises the following steps: S1, raw material crushing and screening: selecting industrial solid waste as the raw material of the full solid waste cementitious material, crushing the industrial solid waste through a crushing device, and then screening to obtain fine particles of the industrial solid waste; S2, fine grinding treatment: fine grinding treatment of the fine particles of the industrial solid waste in S1 to obtain industrial solid waste powder; S3, powder activation treatment: all or part of the industrial solid waste powder in S2 is subjected to physical activation, but not for the purpose of improving the specific surface area; S4, key active mineral addition: adding key active minerals to the activated industrial solid waste powder in S3 to prepare a cementitious material; S5, preparation of standard paste test block: preparing the cementitious material in S4 into a standard paste test block; S6, performance test: testing the early performance of the full solid waste cementitious material over time on the standard paste test block in S5, and adjusting the process parameters of the foregoing steps to obtain the process parameters of the full solid waste cementitious material corresponding to the best early performance parameters.

2. The method of improving early age properties of a full solid waste cementitious material according to claim 1, wherein The industrial solid waste in S1 is at least two of steel slag, blast furnace slag, ferroalloy slag, silicon-manganese slag, industrial by-product gypsum, sintering dust removal ash, fly ash and calcined coal gangue, and the mass of the industrial solid waste accounts for more than 30% of the total mass of the cementitious material.

3. The method of improving early age properties of a full-solid waste cementitious material according to claim 1, wherein S2 each industrial solid waste powder specific surface area > 350 m 2 / kg.

4. The method of improving early age properties of a full-solid waste cementitious material according to claim 1, wherein The physical activation in S3 is achieved by improving the dissociation degree and exposure degree of key mineral components, and optimizing the raw material ratio and introducing key mineral components to optimize the process performance of the cementitious material.

5. The method of improving early age properties of a full solid waste cementitious material according to claim 4, characterized in that, The improvement of the dissociation degree and exposure degree of the key mineral components is achieved by improving the specific surface area of the cementitious material and dissociating and exposing the active sites of the key minerals, wherein the specific surface area of the cementitious material is improved by single solid waste fine grinding, and the active sites of the key minerals are dissociated and exposed by mixing and semi-autogenous grinding or stirring of multiple solid wastes, and the hardness difference of the constituent minerals in the solid waste is utilized to dissociate and expose the active sites of the key minerals.

6. The method of improving early age properties of a full solid waste cementitious material according to claim 4, wherein The optimization of the raw material ratio and the introduction of the key components improve the content of the key and active minerals without changing the overall mineral composition of the raw material, and the mass of the introduced key components accounts for ≤15% of the total mass of the cementitious material, and the mass fraction of the key and active minerals is improved by ≤10%.

7. The method of improving early age properties of a full solid waste cementitious material according to claim 5, wherein The single solid waste fine grinding refers to fine grinding of industrial solid wastes such as steel slag, blast furnace slag, ferroalloy slag, silicon-manganese slag, industrial by-product gypsum, sintering dust removal ash, fly ash and calcined coal gangue, and the specific surface area after fine grinding is improved by ≤55% compared with that before fine grinding.

8. The method of improving early age properties of a full solid waste cementitious material according to claim 5, wherein, The multiple solid waste mixing semi-autogenous grinding refers to mixing and fine grinding of two or more of industrial solid wastes such as steel slag, blast furnace slag, ferroalloy slag, silicon-manganese slag, industrial by-product gypsum, sintering dust removal ash, fly ash and calcined coal gangue, and the dissociation degree of key active minerals such as calcium-containing minerals, silicate minerals and sulfate minerals is improved by ≥50% through mixing and semi-autogenous grinding, and the intergrowth rate with calcium ferrite and magnesium ferrite minerals is ≤40%.

9. The method of improving early age properties of a full solid waste cementitious material according to claim 5, wherein, The stirring and mixing are achieved by mechanical, gas, gravity or centrifugal force.

10. The method of improving early age properties of a full solid waste cementitious material according to claim 5, wherein, The 1d compressive strength of the standard neat paste test block is increased by more than 100%, the 1d final compressive strength is greater than 32 MPa, the 1d flexural strength is increased by more than 100%, and the 1d final flexural strength is all greater than 18 MPa, most of which is greater than 21 MPa; the 3d compressive strength is increased by more than 100%, the 3d final compressive strength is all greater than 45 MPa, the 3d flexural strength is increased by more than 100%, and the 3d final flexural strength is all greater than 29 MPa; the 28d compressive strength is increased by more than 100%, the 28d final compressive strength is all greater than 90 MPa, the highest of which exceeds 100 MPa, the 28d flexural strength is increased by more than 100%, and the 28d final flexural strength is greater than 35 MPa, most of which is greater than 50 MPa; the cementing material pH value is 12.0-12.3, and the manufacturing cost of the cementing material is 30-80 yuan / ton.

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