CN113135704B - Activation utilization method for adverse factors of steel slag stability under autoclaved condition - Google Patents

Activation utilization method for adverse factors of steel slag stability under autoclaved condition Download PDF

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CN113135704B
CN113135704B CN202110566316.7A CN202110566316A CN113135704B CN 113135704 B CN113135704 B CN 113135704B CN 202110566316 A CN202110566316 A CN 202110566316A CN 113135704 B CN113135704 B CN 113135704B
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steel slag
slag
autoclaved
barium
condition
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CN113135704A (en
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郑琪
赵风清
张玉婷
潘仕文
赵全胜
李配欣
李莎
张志国
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Hebei University of Science and Technology
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Hebei University of Science and Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/245—Curing concrete articles
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • C04B18/142—Steelmaking slags, converter slags
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Processing Of Solid Wastes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention provides an activation utilization method for the stability problem of steel slag under an autoclaved condition, which comprises the following steps: mixing the steel slag powder, the tailings, the cement, the waste incineration fly ash, the barium slag, the ammonium dihydrogen phosphate and the magnesium sulfate, then adding water to uniformly mix the materials to prepare a green brick; pre-curing the green brick under the wet heat condition of 50-55 ℃, and then performing autoclaved curing under the condition of 180-200 ℃. The invention eliminates the volume expansibility of f-CaO in the steel slag, can obviously improve the problem of poor stability of the steel slag, reduces the activity loss of the steel slag and optimizes the production process of steel slag autoclaved building materials. The invention can shorten the production process flow of the autoclaved brick while improving the stability of the steel slag, greatly reduce the consumption of cement and improve the addition amount of the steel slag.

Description

Activation utilization method for adverse factors of steel slag stability under autoclaved condition
Technical Field
The invention relates to an activation utilization method for the stability problem of steel slag under an autoclaved condition, which improves the stability of a test block, enhances the strength of a system and prepares an autoclaved building material with excellent performance by carrying out pre-curing and modification on a steel slag-tailing-cement system under the autoclaved condition.
Background
The steel slag is a byproduct in the steel manufacturing process, the steel slag generation amount per year in China can reach 1 hundred million tons, the huge generation amount does not have matched high utilization rate, more than 70 percent of the steel slag cannot be effectively utilized, and the stockpiling amount of the steel slag is continuously increased. The method not only occupies the land and poses serious threats to the ecological environment and safety, but also causes huge resource waste. The utilization rate of the steel slag is improved, high-quality safe utilization is realized, and the steel slag is not only a preoccupation of waste producing enterprises, but also a major national demand.
Using steel slag similar to cement C2S、C3The S mineral component makes the concrete have great progress in the field of road engineering and also has a function in the aspect of building wall materialsAnd (5) determining and researching. However, because the steel slag contains f-CaO and f-MgO, the steel slag undergoes hydration reaction when meeting water to generate hydroxide, so that the test block expands by 1.5-2 times, and the utilization rate of the steel slag is seriously influenced. Chinese patent CN103524058A introduces a method for processing the stability of steel slag, provides a method for processing the stability of steel slag at normal temperature or lower temperature, increases the doping amount of steel slag in building material products, and provides technical support for realizing large-scale utilization of steel slag. Chinese patent CN104909634A introduces a autoclaved brick prepared from large-dosage steel slag powder and a preparation method thereof, and proposes that the brick is pre-cured under the action of an inhibitor, so that the problem of poor stability caused by steel slag is solved, the strength of the steel slag autoclaved test block is effectively improved, but the loss of the gelling activity of the steel slag is large.
Aiming at the problems, the invention realizes the stability treatment and utilization of the steel slag by using the pre-curing and the synergy of the modifier and the auxiliary agent in the production process of the autoclaved brick, so that the free oxides in the steel slag, the fly ash, the barium slag and the auxiliary agent are subjected to hydration reaction to generate insoluble double salt, the free oxides harmful to the material are converted into beneficial minerals, the mechanical property of the material is improved, the separate pretreatment cost of the stability of the steel slag is saved, the process flow is shortened, the dosage of cement and lime is greatly reduced, and the addition amount of the steel slag is increased.
Disclosure of Invention
The invention provides a method for activating and utilizing steel slag stability under an autoclaved condition, which adopts the technical scheme that: mixing the steel slag powder, the tailings, the cement, the waste incineration fly ash, the barium slag, the ammonium dihydrogen phosphate and the magnesium sulfate, then adding water to uniformly mix the materials to prepare a green brick; pre-curing the green brick under the condition of moist heat at 50-55 ℃, and then performing autoclaved curing under the condition of 180-200 ℃.
In the method, the material ratio by weight is as follows: 30-40% of steel slag powder, 43-52% of tailings, 4-5% of cement, 3.5-8.5% of waste incineration fly ash, 1-3% of barium slag, 2.5-3.5% of ammonium dihydrogen phosphate and 0.5-1.5% of magnesium sulfate.
The steel slag powder is obtained by crushing, thermally braising, magnetically separating and deironing converter steel slag, drying and grinding, and the specific surface area is 400 m2/kg～500m2Per kg, the content of free calcium oxide is 2 to 4 percent.
The waste incineration fly ash is generated in the waste incineration process and mainly comprises 16-36% of CaO and SiO2 5%～20%、Al2O3 1%～13%、MgO 1%～4%、K2O 0.5%～8%、Na2O 1%～4%、Fe2O3 1-4%, inorganic chloride and sulfate, etc.
The barium residue is waste residue generated in the process of preparing barium sulfate, and is ground to a specific surface area of 300m2/kg～450m2Per kg, the content of silicon dioxide is 20-30 percent, and the content of barium oxide is 15-20 percent.
The invention has the beneficial effects that: the invention realizes the activated utilization of the stability problem of the steel slag by using the modes of pre-curing and the synergy of the modifier and the auxiliary agent in the production process of the autoclaved brick, adopts the ideas of thinning and using and is completely opposite to the traditional thinking of eliminating the volume expansibility (namely the problem of poor volume stability) of the f-CaO in the steel slag (blocking and eliminating). The invention aims to reduce the activity loss of the steel slag and realize the best use of the steel slag. The invention can shorten the production process flow of the autoclaved brick while improving the stability of the steel slag, greatly reduce the consumption of cement and improve the addition amount of the steel slag.
Detailed Description
The invention will be described in detail with reference to the following examples, and the steam-pressing brick test is described in GB/T2542-2012 "method for testing wall-building bricks". The specific surface area of the barium slag used in the embodiment is 365m2Per kg, specific surface area of steel slag 443m2/kg。
Example one
Measuring 40% of steel slag, 43.5% of tailings, 4% of cement, 7.5% of waste incineration fly ash, 1% of barium slag, 2.5% of ammonium dihydrogen phosphate and 1.5% of magnesium sulfate, adding the measured materials into a stirrer, adding a proper amount of water, uniformly stirring, and pressing into a green brick; the water-material ratio is 0.09, and the molding pressure is 30 MPa.
And carrying out damp-heat curing on the green bricks at the temperature of 50-55 ℃ for 8h, and then carrying out curing by an autoclaved system of heating for 3.5h, keeping the temperature at 180 ℃ for 4h and naturally cooling.
Example two
Measuring 35% of steel slag, 45% of tailings, 4.5% of cement, 3.5% of waste incineration fly ash, 3% of barium slag, 3.5% of ammonium dihydrogen phosphate and 1.5% of magnesium sulfate, adding the measured materials into a stirrer, adding a proper amount of water, uniformly stirring, and pressing into a green brick; the water-material ratio is 0.09, and the molding pressure is 30 MPa.
And carrying out damp-heat curing on the green bricks at the temperature of 50-55 ℃ for 8h, and then carrying out curing by an autoclaved system of heating for 3.5h, keeping the temperature at 190 ℃ for 4h and naturally cooling.
EXAMPLE III
Measuring 40% of steel slag, 41.5% of tailings, 4% of cement, 5% of waste incineration fly ash, 3% of barium slag, 2.5% of ammonium dihydrogen phosphate and 1% of magnesium sulfate, adding the measured materials into a stirrer, adding a proper amount of water, uniformly stirring, and pressing into a brick blank; the water-material ratio is 0.09, and the molding pressure is 30 MPa.
And carrying out damp-heat curing on the green bricks at the temperature of 50-55 ℃ for 8h, and then carrying out curing by an autoclaved system of heating for 3.5h, keeping the temperature at 100 ℃ for 4h and naturally cooling.
Example four
Measuring 30% of steel slag, 51.5% of tailings, 4.5% of cement, 8% of waste incineration fly ash, 2% of barium slag, 3.5% of ammonium dihydrogen phosphate and 0.5% of magnesium sulfate, adding the measured materials into a stirrer, adding a proper amount of water, uniformly stirring, and pressing into a green brick; the water-material ratio is 0.09, and the molding pressure is 30 MPa.
And carrying out moist heat curing on the green bricks for 8 hours at the temperature of 50-55 ℃, and then carrying out curing by an autoclave system of heating for 3.5 hours, keeping the temperature at 180 ℃ for 4 hours and naturally cooling.
EXAMPLE five
Measuring 35% of steel slag, 46% of tailings, 4.5% of cement, 6% of waste incineration fly ash, 2% of barium slag, 2.5% of ammonium dihydrogen phosphate and 1.5% of magnesium sulfate, adding the measured materials into a stirrer, adding a proper amount of water, uniformly stirring, and pressing into a green brick; the water-material ratio is 0.09, and the molding pressure is 30 MPa.
And carrying out moist heat curing on the green bricks for 8 hours at the temperature of 50-55 ℃, and then carrying out curing by an autoclave system of heating for 3.5 hours, keeping the temperature at 200 ℃ for 4 hours and naturally cooling.
EXAMPLE six
Measuring 30% of steel slag, 50% of tailings, 5% of cement, 8.5% of waste incineration fly ash, 3% of barium slag, 3% of ammonium dihydrogen phosphate and 0.5% of magnesium sulfate, adding the measured materials into a stirrer, adding a proper amount of water, uniformly stirring, and pressing into a brick blank; the water-material ratio is 0.09, and the molding pressure is 30 MPa.
And carrying out damp-heat curing on the green bricks at the temperature of 50-55 ℃ for 8h, and then carrying out curing by an autoclaved system of heating for 3.5h, keeping the temperature at 200 ℃ for 4h and naturally cooling.
Comparative example
Measuring 30% of steel slag, 65% of tailings and 5% of cement, adding the measured materials into a stirrer, adding a proper amount of water, uniformly stirring, and pressing into a green brick; the water-material ratio is 0.09, and the molding pressure is 30 MPa.
And carrying out damp-heat curing on the green bricks at the temperature of 50-55 ℃ for 8h, and then carrying out curing by an autoclaved system of heating for 3.5h, keeping the temperature at 200 ℃ for 4h and naturally cooling.
Figure 23297DEST_PATH_IMAGE001

Claims (4)

1. An activation utilization method for adverse factors of steel slag stability under an autoclaved condition is characterized by comprising the following steps: mixing the steel slag powder, the tailings, the cement, the waste incineration fly ash, the barium slag, the ammonium dihydrogen phosphate and the magnesium sulfate, then adding water to uniformly mix the materials to prepare a green brick; pre-curing the green bricks under the wet and hot condition of 50-55 ℃, and then performing autoclaved curing under the condition of 180-200 ℃; 30-40% of steel slag powder, 43-52% of tailings, 4-5% of cement, 3.5-8.5% of waste incineration fly ash, 1-3% of barium slag, 2.5-3.5% of ammonium dihydrogen phosphate and 0.5-1.5% of magnesium sulfate.
2. The method of claim 1, wherein: the steel slag powder is obtained by crushing, thermally braising, magnetically separating and deironing converter steel slag, drying and grinding, and the specific surface area is 400 m2/kg～500m2Per kg, the content of free calcium oxide is 2 to 4 percent.
3. The method of claim 1, wherein the step of removing the metal oxide is performed by a chemical vapor deposition processIn the following steps: the waste incineration fly ash is generated in the waste incineration process and mainly comprises 16-36% of CaO and SiO2 5%～20%、Al2O3 1%～13%、MgO 1%～4%、K2O 0.5%～8%、Na2O 1%～4%、Fe2O3 1%～4%。
4. The method of claim 1, wherein: the barium slag is waste slag generated in the process of preparing barium sulfate, and is ground until the specific surface area is 300m2/kg～450m2Per kg, the content of silicon dioxide is 20-30 percent, and the content of barium oxide is 15-20 percent.
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CN115677246B (en) * 2021-07-23 2024-03-01 中国科学院过程工程研究所 Method for preparing cement admixture by utilizing steel slag
CN114349413B (en) * 2022-03-18 2022-05-27 中国科学院生态环境研究中心 Barium slag harmless recycling treatment method and prepared building material
CN115259826B (en) * 2022-09-29 2022-12-27 河北化工医药职业技术学院 Solid waste base 3D printing material
CN116408330B (en) * 2023-06-01 2023-08-04 北京建工环境修复股份有限公司 Co-processing method of barium slag, fly ash and dangerous waste incinerator slag

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DE1104419B (en) * 1957-02-14 1961-04-06 Nikolaus Wilhelm Knauf Method and device for the production of building structures
CN100455533C (en) * 2006-04-21 2009-01-28 华南理工大学 A novel masonry cement
CN103524058B (en) * 2013-10-10 2015-09-02 河北科技大学 A kind of steel slag stability treatment process
CN104909634A (en) * 2015-06-04 2015-09-16 河北科技大学 Autoclaved brick prepared from large-mixing-amount steel slag powder and preparation method of autoclaved brick

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