CN110818356B - Preparation method of high-performance carbonized reinforced concrete - Google Patents

Preparation method of high-performance carbonized reinforced concrete Download PDF

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CN110818356B
CN110818356B CN201911212719.0A CN201911212719A CN110818356B CN 110818356 B CN110818356 B CN 110818356B CN 201911212719 A CN201911212719 A CN 201911212719A CN 110818356 B CN110818356 B CN 110818356B
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steel slag
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reinforced concrete
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CN110818356A (en
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刘志超
曾海马
王发洲
张秀贞
何永佳
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Wuhan University of Technology WUT
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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
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04Portland cements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/245Curing concrete articles
    • 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
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06Aluminous cements
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017Aspects relating to the protection of the environment
    • 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
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a preparation method of high-performance carbonized reinforced concrete, which comprises the following steps: mixing steel slag, a hydraulic cementing material, a carbonization reinforcing phase and quartz sand, adding water and a water reducing agent for mixing, and pouring and molding the mixed slurry; sealing and curing the formed product for 12-24 hours, then removing the mold, and carrying out drying pretreatment; subjecting the dried product to CO2Carbonizing and curing for 12-24 hours in a carbonization kettle with atmosphere of 0.1-0.5MPa to obtain the steel slag product. The high-performance carbonized reinforced concrete prepared by the invention has excellent working performance, fully utilizes the hydration and carbonization synergistic effect of hydraulic cementing materials and steel slag, can reach 100MPa of compressive strength in a short time, simultaneously obviously improves the utilization rate of the steel slag, and can largely solidify and store CO2The method has great environmental benefits, is beneficial to developing green building materials, and can develop roads sustainably.

Description

Preparation method of high-performance carbonized reinforced concrete
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of high-performance carbonized reinforced concrete.
Background
At present, the annual steel yield of China accounts for 1/5 of the worldwide steel industry, the discharge amount of steel slag as the waste slag generated in the steel making process is about 15 percent of the steel yield, the annual discharge amount of the steel slag in China is up to one hundred million tons, but the utilization rate of the steel slag is lower, and the comprehensive utilization rate is only 20 percent. Compared with the effective utilization rate of 65 percent in Europe, the current situation of the utilization of American emission and utilization which are basically balanced, a large amount of steel slag in China is stacked and placed, thereby occupying cultivated land and causing serious water pollution and environmental pollution. Therefore, the utilization rate of the steel slag is improved at present.
The steel slag has low utilization rate and low utilization degree in the current utilization state of China, is mainly used for road and engineering backfill materials, is partially used for concrete mineral admixtures, and has limited utilization approaches and single utilization technology. The steel slag has large component fluctuation, high content of free calcium oxide and poor volume stability, so that when the steel slag is applied to roads, the steel slag is easy to crack due to volume expansion after engineering backfilling, and the engineering safety is seriously influenced; when the material is applied to concrete, the defects such as cracks and the like are easily generated, and the performance of the concrete is influenced.
The steel slag contains a large amount of alkaline oxides, has a certain hydration activity and excellent carbonization activity, and can endow steel slag concrete with excellent mechanical strength by a carbonization technology. However, the existing carbonization forming method is single, mainly adopts compression forming, and limits the application range of the steel slag product to a certain extent. In a few processes, steel slag is used for replacing part of cement to prepare the carbonizable concrete material through pouring forming, but the general water-cement ratio is higher, so that the CO is seriously restricted2The diffusion of the gas into the product and the progress of the carbonization reaction lead to low mechanical strength of the concrete.
Disclosure of Invention
The invention aims to provide a method for obtaining high-performance carbonized reinforced concrete while realizing resource utilization of steel slag, which provides demolding strength by utilizing early high hydration activity of a hydraulic cementing material and performs carbonization reinforcement on the concrete by utilizing high carbonization activity of the steel slag; improves the traditional compression molding process and simultaneously obtains a fast-hardening, high-strength and environment-friendly composite carbonized product.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of high-performance carbonized reinforced concrete comprises the following steps:
1) mixing steel slag, a hydraulic cementing material, a carbonization reinforcing phase and quartz sand, adding water and a water reducing agent for mixing, and pouring and molding the mixed slurry;
2) sealing and curing the formed product for 12-24 hours, then removing the mold, and carrying out drying pretreatment;
3) subjecting the dried product to CO2Carbonizing and curing for 12-24 hours in a carbonization kettle with atmosphere of 0.1-0.5MPa to obtain the steel slag product.
According to the scheme, the content of each raw material in each cubic meter of concrete obtained in the step 1 is as follows: hydraulic binder: 157.2-33.3kg, steel slag: 898.5-1054.8kg, carbonization reinforcing phase: 67.4-22.2kg, quartz sand: 1060kg, water: 175.2-176.7kg, water reducing agent: 44.9-45.3 kg.
According to the scheme, the steel slag is converter steel slag; it is composed ofThe content of medium free calcium oxide is less than or equal to 5 wt%, the content of metallic iron is less than or equal to 6 wt%, and the specific surface area of the steel slag is more than or equal to 300m2In terms of/kg. The steel slag comprises the following main components in percentage by weight: al (Al)2O3:3%-7%;SiO2:14%-27%; CaO:31%-65%;Fe2O3:11%-17%。
According to the scheme, the water reducing agent is a composite water reducing agent formed by mixing a polycarboxylic acid high-efficiency water reducing agent and a sodium citrate retarder.
According to the scheme, the diameter distribution of the quartz sand grains is 300-1100 mu m.
According to the scheme, the carbonization reinforcing phase is at least one of polyethylene glycol, polyvinyl alcohol, chitosan and amorphous silica materials.
According to the scheme, the hydraulic cementing material is at least one of ordinary portland cement and sulphoaluminate cement.
According to the scheme, the drying treatment temperature in the step 2 is 40-50 ℃, the relative humidity is 20-40%, and the drying time is 6-12 hours.
According to the scheme, the temperature in the carbonation curing container in the step 3 is 5-50 ℃, the relative humidity is 50-100%, and the concentration of carbon dioxide is 10-100%.
The invention provides high-performance carbonized reinforced concrete with an extremely low water-to-gel ratio, wherein a cementing material comprises 90-95% of steel slag and 5-10% of hydraulic cementing material by mass, the early structural strength is provided by utilizing the hydration hardening mechanism of the hydraulic cementing material, and the concrete is carbonized and reinforced after being sealed, maintained and demoulded for 12-24 hours, so that the carbonization activity of the steel slag is fully exerted, and the strength of the concrete is further improved. The prepared high-performance carbonized reinforced concrete has excellent working performance, fully utilizes the hydration and carbonization synergistic action of cement and steel slag, can reach the compressive strength of 100MPa in a short time, obviously improves the utilization rate of the steel slag, and can cure and store CO in large quantity2The method has great environmental benefits, is beneficial to developing green building materials, and can develop roads sustainably.
The high-performance carbonized reinforced concrete has the following advantages:
1. the molding method of the traditional carbonized product is improved, the traditional carbonized product adopts a compression molding method, the molding process difficulty is higher, and the size expansibility of the product is limited. The invention adopts pouring molding, reduces the process difficulty and is beneficial to the preparation of large-size products.
2. The strength is developed quickly and the strength grade is high. In the invention, the strength is improved by 20MPa after carbonization for 6 hours. And the strength continues to increase along with the increase of the carbonization time, and compared with the traditional hydration process, the strength development is fast and the strength grade is high.
3. Based on the matrix structure design with the closest packing of particles. According to the invention, through the optimized design of the particle sizes of the gelling component and the fine aggregate, the high-density stacking of the matrix structure is realized, the product with low cement consumption and high early strength is obtained, and the cementing effect of cement hydration is fully exerted.
4. Low water-gel ratio, and is favorable for CO2The gas enters the concrete to promote the carbonization reaction.
5. Efficient storage of solidified CO2. The steel slag contains more alkaline oxides, has excellent carbonization activity and can react with CO2Reaction to form CaCO3And solidifying the carbon dioxide.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
The high-performance carbonized reinforced concrete provided by the invention comprises the following raw materials in per cubic meter of concrete: hydraulic binder: 157.2-33.3kg, steel slag: 898.5-1054.8kg, carbonization reinforcing phase: 67.4-22.2kg, quartz sand: 1060kg, water: 175.2-176.7kg, water reducing agent: 44.9-45.3 kg.
In order to meet the construction requirements, the water reducing agent is a composite water reducing agent formed by mixing a polycarboxylic acid high-efficiency water reducing agent and a sodium citrate retarder.
In order to better improve the performance of the concrete, the steel slag is selected to have the particle size distribution D50 of 6-9 mu m, and the cement is selected to be ordinary portland cement with the strength grade of 52.5. The invention adopts the method that the quartz sand with the grain diameter of 300-1100 mu m is doped in the mortar per cubic meter.
The preparation process comprises the following steps: the preparation process of the invention is mainly divided into three steps as follows:
1) mixing steel slag, a hydraulic cementing material, a carbonization reinforcing phase and quartz sand, adding water and a water reducing agent for mixing, and pouring and molding the mixed slurry;
2) sealing and curing the formed product for 12-24 hours, then removing the mold, and carrying out drying pretreatment;
3) subjecting the dried product to CO2Carbonizing and curing for 12-24 hours in a carbonization kettle with atmosphere of 0.1-0.3MPa to obtain the steel slag product.
Example 1
The high-performance carbonized reinforced concrete is prepared by the following processes:
Figure BDA0002298584340000031
Figure BDA0002298584340000041
according to the drying time: 28 hours
Carbonization time: 12 hours;
carbonization pressure: 0.3 MPa;
sand volume fraction: 40 percent.
Preparing raw materials, wherein the four different mixing amounts are respectively as follows: 157.2 g, 78.6 g, 33.3 g and 0g of hydraulic cementing material, 898.5 g, 1010.8 g, 1054.8 g and 1137.6g of steel slag, 67.4 g, 33.7 g, 22.2 g and 0g of carbonized reinforcing phase and 1060g of quartz sand are all mixed uniformly, then 175.2 g, 176.7 g, 177.5g of water and a mixture prepared by mixing 44.9 g, 45.3 g and 45.5g of water reducing agent are added, the mixture is uniformly stirred and poured into a mold for molding; then sealing and maintaining for 24 hours, and placing the product in a drying oven for drying for 28 hours after demoulding; and curing for 12 hours in a carbonization curing chamber with the relative humidity of 85 percent, the carbon dioxide concentration of 95 percent and the air pressure of 0.4MPa (0.3 MPa higher than the external atmospheric pressure) at the temperature of 20 ℃ to obtain the composite reinforced carbonized product. The performance parameters of the products with different steel slag mixing amounts are shown in the following table.
Amount of steel slag 80% 90% 95% 100%
Compressive strength before carbonization/MPa 26.65 15.35 8.30 8.10
Compressive strength/MPa after carbonization 101.87 97.68 78.28 70.83
Example 2
The high-performance carbonized reinforced concrete is prepared by the following processes:
Figure BDA0002298584340000042
according to the mixing amount of the steel slag: 90 percent;
drying time: 27 hours;
carbonization time: 12 hours;
carbonization pressure: 0.3 MPa.
Preparing raw materials, preparing mortar samples according to the content of each component in the table, uniformly stirring, and pouring into a mold for molding; then sealing and curing for 24 hours, and placing the product in a drying oven for drying for 27 hours after demolding; curing for 12 hours in a carbonization curing chamber with the temperature of 20 ℃, the relative humidity of 80 percent, the carbon dioxide concentration of 99.8 percent and the air pressure of 0.4MPa (0.3 MPa higher than the external atmospheric pressure) to obtain the composite reinforced carbonized product. The performance parameters of the steel slag products with different volume fractions of the aggregate are shown in the following table.
Aggregate volume fraction 0% 20% 30% 40%
Compressive strength before carbonization/MPa 8.1 10.4 12.30 15.35
Compressive strength/MPa after carbonization —— 79.53 90.15 97.68
Example 3
The high-performance carbonized reinforced concrete is prepared by the following processes:
Figure BDA0002298584340000051
according to the mixing amount of the steel slag: 80 percent;
drying time: 11 hours;
carbonization time: 12 hours;
carbonization pressure: 0.1, 0.2, 0.3 and 0.4 MPa.
Preparing raw materials, preparing mortar samples according to the content of each component in the table, uniformly stirring, and pouring into a mold for molding; then sealing and maintaining for 24 hours, and placing the product in a drying oven for drying for 11 hours after demolding; curing the mixture for 12 hours in a carbonization curing chamber with the air pressure of 0.1, 0.2, 0.3 and 0.4MPa at the temperature of 20 ℃ and the relative humidity of 60 percent and the carbon dioxide concentration of 99.8 percent respectively to obtain the composite reinforced carbonized product. The test shows that the performance parameters of the steel slag products under different carbonization pressures are shown in the table below.
Carbonization pressure/MPa 0.1 0.2 0.3 0.4
After carbonizationCompressive strength/MPa 35 44.74 47.9 48.68
Example 4
The high-performance carbonized reinforced concrete is prepared by the following processes:
Figure BDA0002298584340000052
according to the mixing amount of the steel slag: 80 percent;
drying time: 4.8, 12, 16, 20, 24, 84 hours;
carbonization time: 12 hours;
carbonization pressure: 0.3 MPa.
Preparing raw materials, preparing mortar samples according to the content of each component in the table, uniformly stirring, and pouring into a mold for molding; then sealing and curing for 24 hours, and respectively placing the materials in a drying oven for drying for 4, 8, 12, 16, 20, 24 and 84 hours after demolding; and (3) curing for 12 hours in a carbonization curing chamber at 25 ℃ and with the relative humidity of 70 percent, the carbon dioxide concentration of 99.8 percent and the air pressure of 0.4MPa (0.3 MPa higher than the external atmospheric pressure) to obtain the composite reinforced carbonized product. The test results show that the performance parameters of the steel slag products with different pre-drying time are shown in the table below.
Predrying time/h 4 8 12 16 20 24 84
Compressive strength before carbonization/MPa 8 11.43 14.87 16.4 18.93 22.37 23.45
Compressive strength/MPa after carbonization 30.2 40.35 54.05 65.95 69.83 79.02 63.13
Example 5
The high-performance carbonized reinforced concrete is prepared by the following processes:
Figure BDA0002298584340000061
according to the mixing amount of the steel slag: 80 percent;
drying water loss rate: 63% -67%;
carbonization time: 12 hours;
carbonization pressure: 0.3 MPa;
sand volume fraction: 40 percent.
Preparing raw materials, preparing mortar samples according to the content of each component in the table, uniformly stirring, and pouring into a mold for molding; then sealing and maintaining for 24 hours, and after demolding, respectively placing the materials in a drying oven for drying until the water loss rate is 63% -67%; and (3) curing for 12 hours in a carbonization curing chamber at 25 ℃ and with the relative humidity of 75 percent, the carbon dioxide concentration of 99.8 percent and the air pressure of 0.4MPa (0.3 MPa higher than the external atmospheric pressure) to obtain the composite reinforced carbonized product. The test shows that the performance parameters of the steel slag products with different mixing amounts of the carbonization reinforcing phase are shown in the following table.
Mixing amount of carbonized reinforcing phase 0% 15% 30% 40%
Compressive strength before carbonization/MPa 38.6 27 18.1 15
Compressive strength/MPa after carbonization 80.13 78.38 85.9 96.75

Claims (7)

1. The preparation method of the high-performance carbonized reinforced concrete is characterized by comprising the following steps:
1) mixing steel slag, a hydraulic cementing material, a carbonization reinforcing phase and quartz sand, adding water and a water reducing agent for mixing, and pouring and molding the mixed slurry; wherein, the contents of the raw materials in each cubic meter of concrete are respectively as follows: hydraulic binder: 157.2-33.3kg, steel slag: 898.5-1054.8kg, carbonization reinforcing phase: 67.4-22.2kg, quartz sand: 1060kg, water: 175.2-176.7kg, water reducing agent: 44.9-45.3 kg; the carbonization reinforcing phase is at least one of polyethylene glycol, polyvinyl alcohol, chitosan and amorphous silica materials;
2) sealing and curing the formed product for 12-24 hours, then removing the mold, and carrying out drying pretreatment;
3) subjecting the dried product to CO2Carbonizing and curing for 12-24 hours in a carbonization kettle with atmosphere of 0.1-0.5MPa to obtain the steel slag product.
2. The method for preparing the high-performance carbonized-reinforced concrete according to claim 1, wherein the steel slag is converter steel slag; wherein the content of free calcium oxide is less than or equal to 5 wt%, the content of metallic iron is less than or equal to 6 wt%, and the specific surface area of the steel slag is more than or equal to 300m2/kg。
3. The method for preparing high-performance carbonized and reinforced concrete according to claim 1, wherein the water reducing agent is a compound water reducing agent prepared by mixing a polycarboxylic acid high-efficiency water reducing agent and a sodium citrate retarder.
4. The method for preparing high performance carbonized reinforced concrete as described in claim 1, wherein said silica sand has a particle size distribution of 300-1100 μm.
5. The method for producing high-performance carbonized-reinforced concrete according to claim 1, wherein said hydraulic binder is at least one of ordinary portland cement and sulphoaluminate cement.
6. The method for preparing high-performance carbonized-reinforced concrete according to claim 1, wherein the drying treatment in step 2 is carried out at a temperature of 40 ℃ to 50 ℃, at a relative humidity of 20% to 40%, and for a drying time of 6 to 12 hours.
7. The method for preparing high-performance carbonized-reinforced concrete according to claim 1, wherein the temperature in the carbonized curing vessel in step 3 is 5 to 50 ℃, the relative humidity is 50 to 100%, and the carbon dioxide concentration is 10 to 100%.
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