CN114751662B - Preparation method of alkaline steel slag activity excitant and steel slag cementing material - Google Patents

Preparation method of alkaline steel slag activity excitant and steel slag cementing material Download PDF

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Publication number
CN114751662B
CN114751662B CN202210331804.4A CN202210331804A CN114751662B CN 114751662 B CN114751662 B CN 114751662B CN 202210331804 A CN202210331804 A CN 202210331804A CN 114751662 B CN114751662 B CN 114751662B
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steel slag
attapulgite
alkaline
sodium silicate
excitant
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CN114751662A (en
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张枥讠华
邵彦凌
丁向群
房延凤
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Fushun Dahuofang Cement Co ltd
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Fushun Dahuofang Cement Co ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/14Cements containing slag
    • C04B7/147Metallurgical slag
    • C04B7/153Mixtures thereof with other inorganic cementitious materials or other activators
    • C04B7/1535Mixtures thereof with other inorganic cementitious materials or other activators with alkali metal containing activators, e.g. sodium hydroxide or waterglass

Abstract

The invention discloses an active excitation of alkaline steel slagA preparation method of a hair-growing agent and a steel slag cementing material, belonging to the technical field of building materials; comprises attapulgite, sodium hydroxide, sodium silicate and slaked lime/carbide slag, wherein the mass ratio of (25-35): (1-3): (5-20): (1-5), and sodium hydroxide and sodium silicate are adsorbed and loaded on the inner pore canal and the surface of the attapulgite; the preparation method comprises preparing sodium hydroxide and sodium silicate into aqueous solution; adding attapulgite into the solution, ultrasonic stirring, drying, pulverizing, and grinding to obtain a specific surface area of not less than 450m 2 Powder/kg; and finally, uniformly mixing the mixture with slaked lime or carbide slag to prepare the alkaline steel slag activity excitant. The excitant creatively utilizes the structural characteristics of the attapulgite, and effectively solves the problems that the conventional excitant is not thoroughly reacted with the steel slag and can not excite the activity of the steel slag to the greatest extent; the finally prepared active mineral (steel slag) admixture concrete has better mechanical strength and working performance.

Description

Preparation method of alkaline steel slag activity excitant and steel slag cementing material
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a basic steel slag activity excitant and a steel slag cementing material.
Background
Steel slag is a byproduct in the steelmaking process and mainly consists of oxides of calcium, iron, silicon, magnesium, a small amount of aluminum, manganese, phosphorus and the like. With the continuous development of the steel industry, the treatment of steel slag and the recycling of waste are increasingly valued in the industry. The steel slag has potential activity because of containing a certain amount of aluminate, silicate and ferroaluminate; the production of cement from steel slag is one of the important ways of comprehensively utilizing steel slag. However, the common steel slag generated in the current steelmaking has the problems of low activity, slow hydration reaction and the like when being applied to cement cementing materials due to high formation temperature and good crystal development; the steel slag is mixed into cement to have a certain effect on the strength of the cementing material, and the steel slag is limited in application in building materials. Only the steel slag is activated in advance, so that the steel slag can be widely applied to the building material industry, and the steel slag-free ordinary cement and concrete have the performance equivalent to or even better than that of the ordinary cement and concrete without the steel slag.
In the prior art, for example, chinese patent application CN113896445a provides a composite steel slag activity activator, a preparation method thereof and steel slag cement, wherein the activator comprises desulfurized gypsum, and further comprises ceramic tile powder, slaked lime and/or alkaline residue. For example, the Chinese patent application CN113860763A provides a steel slag activity excitant and an active steel slag, which contain desulfurized gypsum, alkaline residue and desulfurized ash, wherein the alkaline residue is waste alkaline residue discharged in the alkaline preparation process by adopting an ammonia-soda process. The composite steel slag excitant provided by CN112723789A comprises the following raw materials of calcium sulfate, sodium carbonate, citric acid, polyalcohol amine, silane coupling agent, metal fluoride and the like; the composite steel slag excitant utilizes metal cations and fluoride ions which are ionized by metal fluoride in water, HF is generated by combination, and has etching effect, when the composite steel slag excitant contacts steel slag, components such as tricalcium silicate, dicalcium silicate and the like in the composite steel slag excitant can be hydrolyzed, namely the activity of the steel slag is excited; the polyalcohol amine has complexation, can complex part of etched metal ions, and the calcium sulfate can form the ettringite in the later stage, thereby contributing to the strength of the material.
The prior patent technologies all excite the activity of the steel slag through the synergistic effect of several raw materials, and improve the compressive strength and the flexural strength of the prepared steel slag cement. However, although the above-mentioned excitants can activate the hydration activity of the steel slag, because the steel slag is in a loose porous structure, new products (aluminosilicate, silicate, aluminate gel and other minerals) generated by the reaction of the excitants and the steel slag can be attached to the surface of the steel slag to block the reaction path of active ions, so that the reaction speed is very fast at first, but the hydration reaction is obviously reduced immediately, and even the reaction cannot be carried out; finally, the active ions lose the excitation effect, so that the reaction rate of the alkali-activated cementing material is very low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a basic steel slag activity excitant and a steel slag cementing material, wherein sodium hydroxide and water glass are loaded and adsorbed in an attapulgite surface and an internal pore canal after being compounded, so that release control of the sodium hydroxide and the water glass is realized, the activation rate of the steel slag activity excitant on steel slag is regulated, the progress of the hydration reaction of the steel slag is further controlled, and the adhesion of products on the steel slag surface is avoided; specifically by the following technique.
An alkaline steel slag activity excitant comprises attapulgite, sodium hydroxide, sodium silicate and slaked lime/carbide slag; the attapulgite clay comprises, by mass, sodium hydroxide, water glass, slaked lime/carbide slag= (25-35), 1-3, 5-20 and 1-5, wherein the sodium hydroxide and the sodium silicate are adsorbed and loaded on the inner pore canal and the surface of the attapulgite clay.
According to the alkaline steel slag activity excitant provided by the invention, sodium hydroxide and sodium silicate are adsorbed and loaded by utilizing natural pore channels and uneven surfaces of attapulgite, so that an effective controlled release effect is achieved on the sodium hydroxide and the sodium silicate. When the steel slag and the alkaline steel slag active exciting agent are used in cement mortar or concrete, part of sodium hydroxide and water glass loaded on the surface of the exciting agent are dissolved first and are hydrated with slaked lime/carbide slag and minerals in the steel slag. As the sodium hydroxide and the sodium silicate on the surface of the excitant are consumed by the reaction, the residual sodium hydroxide and the sodium silicate adsorbed in the attapulgite are gradually released from the surface of the attapulgite, and the hydration reaction is continued. The steel slag, the exciting agent and other raw materials of the cement mortar/concrete are gradually and uniformly mixed and continuously stirred, so that the problem that the surfaces of the steel slag and the attapulgite are blocked basically does not exist.
The alkaline steel slag activity excitant provided by the invention can effectively regulate the hydration reaction process of steel slag and the excitant (namely the activation rate of the excitant to the steel slag), avoid a large amount of minerals from blocking reaction channels on the surface of the steel slag, and ensure that the activity of the steel slag is excited to the greatest extent. The attapulgite can be used as a carrier, and can improve the fluidity, slump and other working properties of cement mortar/concrete and improve the later strength to a certain extent.
Preferably, the mass ratio of the attapulgite, the sodium hydroxide, the water glass and the slaked lime/carbide slag is 28:2:16:4.
Preferably, the sodium silicate has a modulus of 1.2 to 2.6; the specific surface area of the slaked lime or carbide slag is more than or equal to 300m 2 /kg; the particle size of the attapulgite is 1-10 mu m.
The invention also provides a preparation method of the alkaline steel slag activity excitant, which comprises the following steps:
s1, weighing sodium hydroxide and sodium silicate proportionally to prepare an aqueous solution, wherein the concentration of the sodium silicate is 0.5-1.5mol/L; weighing the attapulgite, adding the attapulgite into the solution, and stirring the attapulgite for 2 to 3.5 hours at 1500 to 2000rpm with ultrasonic power of 300 to 800W;
s2, taking the mixed solution obtained in the step S1, drying, crushing and grinding to obtain the product with the specific surface area not smaller than 450m 2 Powder/kg;
and S3, weighing the slaked lime or the carbide slag, and uniformly mixing the slaked lime or the carbide slag with the powder obtained in the step S2 to prepare the alkaline steel slag activity excitant.
Preferably, in the step S1, the concentration of the sodium silicate is 1mol/L.
Preferably, in step S1, the ultrasonic stirring parameter is 1800rpm for stirring for 2.5 hours, and the ultrasonic power is 500W.
The invention also provides a steel slag cementing material with specific surface area not less than 450m by using the alkaline steel slag activity excitant 2 And/kg, wherein the raw materials of the alkaline steel slag activator comprise 85-98wt% of steel slag and 2-15wt% of the alkaline steel slag activator.
Preferably, the steel slag is used in an amount of 92wt% and the alkaline steel slag activity activator is used in an amount of 8wt%.
Compared with the prior art, the invention has the following advantages: the invention provides a novel alkaline steel slag activity excitant, which creatively utilizes the structural characteristics of attapulgite, and effectively solves the problems that the conventional excitant is not thoroughly reacted with steel slag and cannot furthest excite the activity of the steel slag; the finally prepared active mineral (steel slag) admixture concrete has better mechanical strength and working performance.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on embodiments of the present invention, are within the scope of the present invention.
The following implementationThe slaked lime and carbide slag used in the examples and comparative examples were purchased from Liaoning Bunge Calif. and Liaoning Shenyang chemical Co., ltd, respectively, and had a specific surface area of not less than 300m 2 /kg; the attapulgite is purchased from Wuhan, and the grain size is 1.2-8.6 mu m; sodium hydroxide and sodium silicate are conventional chemicals purchased on-line; the main component of the steel slag is 29.41wt% CaO and Fe 2 O 3 18.94wt%、SiO 2 18.69wt%、Al 2 O 3 7.48wt%, mgO 5.52wt%, mnO 2.10wt% and other components.
Example 1
The alkaline steel slag activity excitant provided by the embodiment comprises attapulgite, sodium hydroxide, sodium silicate and slaked lime, wherein the mass ratio is 28:2:16:4, and the sodium hydroxide and the sodium silicate are adsorbed and loaded on the inner pore canal and the surface of the attapulgite.
The preparation method of the alkaline steel slag activity excitant comprises the following steps:
s1, weighing sodium hydroxide and sodium silicate according to a proportion to prepare an aqueous solution, wherein the concentration of the sodium silicate is 1mol/L; the attapulgite is weighed and added into the solution, and is ultrasonically stirred for 2.5 hours at 1800rpm, and the ultrasonic power is about 500W;
s2, taking the mixed solution obtained in the step S1, drying in vacuum, crushing and grinding to obtain the product with the specific surface area not smaller than 450m 2 Powder/kg;
s3, weighing slaked lime, crushing, grinding, and uniformly mixing with the powder obtained in the step S2 to prepare the alkaline steel slag activity excitant.
Example 2
The alkaline steel slag activity excitant provided by the embodiment comprises attapulgite, sodium hydroxide, sodium silicate and slaked lime, wherein the mass ratio is 25:1:20:5, and the sodium hydroxide and the sodium silicate are adsorbed and loaded on the inner pore canal and the surface of the attapulgite. The preparation method of the alkaline steel slag activity excitant is the same as that of the example 1.
Example 3
The alkaline steel slag activity excitant provided by the embodiment comprises attapulgite, sodium hydroxide, sodium silicate and slaked lime, wherein the mass ratio of the sodium hydroxide to the sodium silicate is 35:3:5:1, and the sodium hydroxide and the sodium silicate are adsorbed and loaded on the inner pore canal and the surface of the attapulgite. The preparation method of the alkaline steel slag activity excitant is the same as that of the example 1.
Comparative example 1
The alkaline steel slag activity excitant provided in the comparative example comprises sodium hydroxide, sodium silicate and slaked lime, and the mass ratio is 1:8:2 (namely 2:16:4). The three raw materials are directly and simply mixed to prepare the alkaline steel slag activity excitant of the comparative example.
Comparative example 2
The alkaline steel slag activity activator provided in this comparative example uses the same amount of attapulgite, sodium hydroxide, sodium silicate and slaked lime as in example 1. The preparation method of the activator is to directly and simply mix the four raw materials to prepare the alkaline steel slag active activator of the comparative example.
Comparative example 3
The alkaline steel slag activity activator provided in this comparative example uses the same amount of attapulgite, sodium hydroxide, sodium silicate and slaked lime as in example 1. The preparation method of the excitant comprises the following steps:
s1, weighing sodium silicate according to a proportion to prepare 1mol/L aqueous solution; the attapulgite is weighed and added into the solution, and is ultrasonically stirred for 2.5 hours at 1800rpm, and the ultrasonic power is about 500W;
s2, taking the mixed solution obtained in the step S1, drying in vacuum, crushing and grinding to obtain the product with the specific surface area not smaller than 450m 2 Powder/kg;
and S3, weighing sodium hydroxide and slaked lime, crushing, grinding, and uniformly mixing with the powder obtained in the step S2 to prepare the alkaline steel slag activity excitant.
Test example: performance study of alkaline steel slag activity excitant
Uniformly mixing the alkaline steel slag activity excitants prepared in examples 1-3 and comparative examples 1-3 with steel slag to prepare a steel slag mixture, wherein the dosage ratio of the alkaline steel slag activity excitants to the steel slag mixture is 8:92; meanwhile, steel slag which is not excited by an exciting agent is used as a blank control.
According to the detection method in International Standard GB/T51003-2014 'mineral admixture application technical Specification', mixing the steel slag mixture and cement according to the mixing amount of 3:7, taking 315g of cement (Huaxin P.O42.5 Portland cement), 135g of steel slag mixture (or unexcited common steel slag), 1350g of sand (river sand, mud content of 1.7%), adding 225g of water and uniformly mixing; and (3) filling the sample into a test die, removing the die after 1 day, transferring the sample into a standard curing room, and curing the sample for 3, 7 and 28 days to prepare a detection sample.
According to GB/T17671-1999 "cement mortar strength test method: testing the flexural strength and compressive strength values of the test samples when curing to 3d, 7d and 28d, and calculating the obtained activity index; the fluidity of cement mortar was measured with reference to GB/T2419-2005 method for measuring fluidity of cement mortar, and the results are shown in Table 1:
TABLE 1 Performance test results of Cement mortar
By detecting the alkaline steel slag activity excitants of the examples and the comparative examples, the excitants prepared by the methods and the raw materials of the examples 1-3 are found to have more remarkable excitation effect on the steel slag activity; when the dosage of the attapulgite is changed, the distribution condition of sodium hydroxide and sodium silicate on the surface and the inner pore canal of the attapulgite is influenced, the controlled release of the sodium hydroxide and the sodium silicate is further influenced, and finally the activities of the steel slag in early, middle and later stages of mortar and the rate of hydration reaction are influenced. When sodium hydroxide, sodium silicate and slaked lime are simply mixed for use without using attapulgite, although the mechanical strength of cement mortar can be improved rapidly in early stage by obviously exciting the activity of steel slag, the compressive strength and flexural strength of cement mortar in middle and later stages are affected, and the mechanical strength of cement mortar using the activator of the comparative example is obviously inferior to that of cement mortar using the activator of the example.

Claims (6)

1. The alkaline steel slag activity excitant is characterized by comprising attapulgite, sodium hydroxide, sodium silicate and slaked lime or carbide slag; the mass ratio of the four raw materials is 28:2:16:4, and sodium hydroxide and sodium silicate are adsorbed and loaded on the inner pore canal and the surface of the attapulgite;
the modulus of the sodium silicate is 1.2-2.6; the specific surface area of the slaked lime or carbide slag is more than or equal to 300m 2 /kg; the particle size of the attapulgite is 1-10 mu m.
2. A method for preparing the alkaline steel slag activity excitant according to claim 1, which is characterized by comprising the following steps:
s1, weighing sodium hydroxide and sodium silicate proportionally to prepare an aqueous solution, wherein the concentration of the sodium silicate is 0.5-1.5mol/L; weighing the attapulgite, adding the attapulgite into the solution, and stirring the attapulgite for 2 to 3.5 hours at 1500 to 2000rpm with ultrasonic power of 300 to 800W;
s2, taking the mixed solution obtained in the step S1, drying, crushing and grinding to obtain the product with the specific surface area not smaller than 450m 2 Powder/kg;
and S3, weighing the slaked lime or the carbide slag, and uniformly mixing the slaked lime or the carbide slag with the powder obtained in the step S2 to prepare the alkaline steel slag activity excitant.
3. The method for preparing an alkali steel slag activity activator according to claim 2, wherein in the step S1, the concentration of sodium silicate is 1mol/L.
4. The method for preparing the alkaline steel slag activity activator according to claim 2, wherein in the step S1, the ultrasonic stirring parameter is 1800rpm for stirring for 2.5 hours, and the ultrasonic power is 500W.
5. A steel slag cementing material is characterized in that the specific surface area is not less than 450m 2 Kg, which raw materials consist of 85-98wt% of steel slag and 2-15wt% of the alkaline steel slag activity activator according to any one of claims 1-3.
6. The steel slag cementing material according to claim 5, wherein the steel slag is used in an amount of 92wt%, and the alkaline steel slag activity activator is used in an amount of 8wt%.
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CN116715472A (en) * 2023-05-31 2023-09-08 铜陵铜冠建安新型环保建材科技有限公司 Steel slag-based cementing material and preparation method thereof
CN116462439B (en) * 2023-06-20 2023-09-01 石家庄铁道大学 Carbide slag-based low-shrinkage excitant and preparation method and application thereof

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CN102633461A (en) * 2012-03-22 2012-08-15 内蒙古科技大学 Composite gel material and preparation method thereof
CN103724110A (en) * 2013-12-09 2014-04-16 广西科技大学 Slow release ammonium carbonate fertilizer and preparation method thereof
CN106673159A (en) * 2016-12-14 2017-05-17 安徽吉思特智能装备有限公司 Attapulgite-loaded modified poly-silicon ferric sulfate flocculant and preparation method thereof
WO2020188070A1 (en) * 2019-03-21 2020-09-24 Tata Steel Ijmuiden B.V. Method for the manufacture of high-end performance steel slag-based building products
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