CN114873941A - Carbonized steel slag cement strength improver and application method thereof - Google Patents
Carbonized steel slag cement strength improver and application method thereof Download PDFInfo
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- CN114873941A CN114873941A CN202210375997.3A CN202210375997A CN114873941A CN 114873941 A CN114873941 A CN 114873941A CN 202210375997 A CN202210375997 A CN 202210375997A CN 114873941 A CN114873941 A CN 114873941A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/122—Hydroxy amines
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
- C04B28/082—Steelmaking slags; Converter slags
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0231—Carbon dioxide hardening
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
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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
- 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
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Organic Chemistry (AREA)
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a carbonized steel slag cement strength improver and an application method thereof 2 And (6) carbonizing and curing. The cement strength improver for carbonized steel slag can improve CO 2 The solubility in aqueous solution is reduced, thereby not only reducing the steel slag and CO 2 Activation energy of the reaction to accelerate the carbonization reaction and also to promote gas phase CO 2 The diffusion to the inside of the test block ensures that the whole carbonization reaction of the steel slag test block is uniform, thereby improving the strength of the carbonized steel slag cement. By adopting the technical scheme, the method can be used for realizingThe common industrial tail gas is directly used for the carbonization and maintenance of the steel slag, thereby reducing CO in the industrial tail gas 2 Discharge, realize carbon utilization, and can also prepare carbonized steel slag cement, realize steel slag and CO 2 The value of (A) is obtained.
Description
Technical Field
The invention belongs to the technical field of ecological building materials, and particularly relates to a carbonized steel slag cement strength improver and an application method thereof.
Background
The steel slag is industrial waste slag produced in the steel smelting process and is formed by quenching impurity components in pig iron and oxide hot melt (1600 ℃) of elements such as iron, calcium, manganese, magnesium, aluminum and the like in slagging materials. The steel slag generation amount is about 15-20% of steel. The quantity of steel slag produced in China per year is about 1 hundred million tons, the accumulated total quantity is over 10 hundred million tons, and the comprehensive resource utilization rate is lower than 30 percent. The production of building materials is a main way for the resource utilization of steel slag in China.
The main low-activity phase in the steel slag is gamma-dicalcium silicate, and the hydration activity of the gamma-dicalcium silicate is extremely low. Research shows that the gamma-dicalcium silicate can react with CO 2 The reaction forms calcium carbonate, calcium silicate hydrate gel or silica gel to form strength. Therefore, the carbonized steel slag cement with good mechanical property can be prepared by carbonizing and curing the steel slag powder through an accelerated carbonization experiment. Not only effectively utilizes the steel slag as resources, but also absorbs CO 2 The carbon emission of the building material industry is reduced, and the requirement of the national double-carbon strategy is met.
Gamma-dicalcium silicate and CO 2 The reaction comprises three processes: dissolution of calcium ion and CO in dicalcium silicate 2 Dissolved in water and CO 2 Diffuse to the dicalcium silicate surface. Wherein, under normal temperature and pressure, the dissolution rate of calcium ions is low and CO is 2 The low solubility in water (about 0.033mol/L) results in gamma-dicalcium silicate with CO 2 High reaction activation energy and low reaction rate. At the same time, the lower solubility leads to gas phase CO 2 The steel slag test block slowly diffuses into the steel slag test block from a maintenance environment, the phenomenon that the surface carbonization reaction degree of the steel slag test block is high, but the internal carbonization reaction degree is low is caused, so that the steel slag test block is hard in surface and low in strength.
Therefore, in order to improve the mechanical properties of the carbonized steel slag, the prior technical scheme mainly aims to improve the CO 2 Diffusion rate and reduction of reaction activation energy. Such as increasing CO in curing environments 2 The concentration (60-99.9%) of the gas phase CO in the curing environment is increased 2 Pressure (0.5-5 atm), pressurized supercritical method to dissolve CO in advance 2 The method comprises the steps of mixing water and the like. Common CO in industrial tail gas 2 The concentration is 15-40%, such as CO in tail gas of a conventional cement rotary kiln and an oxygen-enriched combustion cement rotary kiln 2 The concentrations were about 15% and 30%, respectively. Maintenance environment with too high CO 2 Concentration and CO 2 Pressure requirement for CO in industrial tail gas 2 Performing trapping, enrichment, boosting, etc. operations significantly increase equipment and technology costs. Simultaneously, the gamma-dicalcium silicate and CO 2 The reaction produces calcium carbonate, and the volume of the product is larger than that of the reactant. Increase of CO 2 Concentration and CO 2 The pressure easily causes the surface carbonization reaction to be fast, the product calcium carbonate reduces the surface pores of the test block, and further increases CO 2 The difficulty of diffusion into the test block results in low strength of the steel slag test block.
Pressurized supercritical process predissolved CO 2 And then the mixture enters mixing water to form a solution similar to the 'sprite'. The method directly introduces reactive CO into the steel slag test block 2 Reducing the CO generated by the carbonization and maintenance of the steel slag 2 The dependence on diffusion. However, supercritical pre-dissolved CO in the mix water 2 In a metastable state, is unbalanced when mixed and stirred with steel slag, CO 2 Quickly escaping from the mixing water. The steel slag test block is internally provided with CO 2 The escape and the rapid volume expansion lead to the occurrence of a large number of cracks and holes, and the strength of the carbonized test piece is low.
Therefore, the development of a method for improving CO content in the curing process of the carbonized steel slag cement is urgently needed 2 Method for reducing solubility in aqueous solution, i.e. reducing steel slag and CO 2 Activation energy of the reaction to accelerate the carbonization reaction and also to promote gas phase CO 2 The diffusion to the inside of the test block ensures that the whole steel slag test block has uniform carbonization reaction and promotes the strength development of the carbonized steel slag cement.
Disclosure of Invention
The invention provides a carbonized steel slag cement strength improver and an application method thereof for solving the technical problems. The cement strength improver for carbonized steel slag can improve CO 2 The solubility in aqueous solution is reduced, thereby not only reducing the steel slag and CO 2 Activation energy of the reaction to accelerate the carbonization reaction and also to promote gas phase CO 2 And the steel slag cement is dispersed into the test block to ensure that the whole steel slag test block has uniform carbonization reaction so as to improve the strength of the carbonized steel slag cement. By adopting the technical scheme, the common industrial tail gas can be directly used for steel slag carbonization and maintenance, so that the content of the industrial tail gas is reducedCO 2 Discharge, realize carbon utilization, can also prepare carbonized steel slag cement, realize steel slag and CO 2 The value of (A) is obtained.
In order to achieve the purpose, the invention adopts the technical scheme that:
the cement strength improver for the carbonized steel slag is monoethanolamine, polyalcohol amine or N-methyl polyalcohol amine or a mixture of the monoethanolamine, the polyalcohol amine and the N-methyl polyalcohol amine.
Preferably, the polyalcohol amine is diethanolamine or triethanolamine, and the N-methyl polyalcohol amine is N-methyl diethanolamine.
Preferably, the mass ratio of the diethanolamine to the triethanolamine or N-methyldiethanolamine is 2.5-1: 1.
Preferably, the grain diameter of the steel slag powder is less than 80 μm, and the specific surface area is more than 400m 2 /kg。
Preferably, the mass content of the elementary iron of the steel slag powder is less than 10 wt%.
The application method of the carbonized steel slag cement strength improver comprises the following steps:
mixing the carbonized steel slag cement strength improver with mixing water uniformly in advance to obtain an aqueous solution of the carbonized steel slag cement strength improver, standing, discharging bubbles in the mixing water, mixing with steel slag, removing a grinding tool, and adopting CO 2 Or containing CO 2 The industrial tail gas is carbonized and maintained.
Preferably, the mass concentration of the aqueous solution of the carbonized steel slag cement strength improver is 5-25%.
Preferably, the mass ratio of the steel slag to the carbonized steel slag cement strength improver is 1000: 12-65.
The carbonized steel slag cement strength improver provided by the invention can improve CO 2 The principles of solubility and diffusion rate are: alcohol amines such as diethanolamine contain a primary amino group-NH 2 Or secondary amino-NH, enabling it to react with CO 2 Reacting to generate carbamate (-NCOO-), wherein the reaction equation is shown as (1). The reaction can be carried out rapidly at normal temperature and pressure or low pressure, and CO 2 The release process is reversible and therefore can act as CO 2 The intermediate reaction with steel slag and gamma-dicalcium silicate improves CO in the curing process of carbonized steel slag cement 2 Solubility and diffusion rate.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts alcohol amine to obviously improve CO 2 The solubility in the water solution accelerates the reaction rate of the gamma-dicalcium silicate in the steel slag carbonization curing process, and improves the generation amount of calcium carbonate, calcium silicate hydrate gel or silica gel; promoting gas phase CO at the same time 2 The diffusion to the inside of the test block ensures that the whole carbonization reaction of the steel slag test block is uniform, and the mechanical property of the carbonized steel slag cement is improved. The technical scheme realizes low-concentration CO at normal temperature and normal pressure 2 The rapid reaction with the steel slag can obviously reduce the cost investment of equipment for carbonizing the steel slag and the like. Meanwhile, if common industrial tail gas is used as CO of the carbonized steel slag cement 2 The method realizes the carbon utilization of the industrial tail gas and has obvious economic and social benefits.
Drawings
FIG. 1 XRD pattern of carbide slag cement curing 1d in example 4.
FIG. 2 is an XRD spectrum of a steel carbide slag cement cured in 1d in comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The chemical composition and phase composition of the steel slag used in all the examples are shown in Table 1. The specific surface area of the steel slag powder is 426m 2 /kg, particle size less than 80 μm.
TABLE 1 chemical composition and phase composition of steel slag powder (%)
The invention provides a carbonized steel slag cement strength improver which is monoethanolamine, polyalcohol amine or N-methyl polyalcohol amine or a mixture of the monoethanolamine, the polyalcohol amine and the N-methyl polyalcohol amine. The polyalcohol amine is diethanolamine or triethanolamine, and the N-methyl polyalcohol amine is N-methyl diethanolamine.
Examples 1-3 in Table 2 are 20% CO concentration 2 Under the condition of normal pressure, the carbonized steel slag cement strength improver improves CO in aqueous solution (1L) 2 Experimental results for solubility.
In the comparative example, the carbonized steel slag cement strength improver is not added. Comparative example 1 was 1L of deionized water. Comparative example 2 1L of deionized water at 5MPa carbon dioxide pressure to obtain pre-dissolved CO using supercritical method 2 Deionized water.
TABLE 2 (unit: g)
In examples 4 to 7, the steel carbide slag cement strength improver is dissolved in water to obtain an aqueous solution of the steel carbide slag cement strength improver, and the solution is left to stand for 20 min. The water solution and the steel slag dry powder are stirred and mixed, and the water-cement ratio is 0.25. The freshly mixed paste was shaped into cubes of 40mm by 40mm, demolded after 24h and washed with 20% CO 2 Curing at normal pressure under the concentration to obtain the carbonized steel slag cement. The formulation of the carbonized steel slag cement is shown in Table 4.
TABLE 4 carbide slag cement ratio (g)
| Steel slag powder | Diethanolamine (DEA) | N-methyldiethanolamine | Triethanolamine | Deionized water | |
| Example 4 | 1000 | 12.5 | -- | -- | 237.5 |
| Example 5 | 1000 | 25 | 25 | -- | 200 |
| Example 6 | 1000 | 42.5 | -- | 20 | 187.5 |
| Example 7 | 1000 | -- | 25 | 25 | 200 |
Comparative example 3 is a mixture of 1000g of steel slag with 250g of water, demoulded 24h after moulding, in 20% CO 2 And (5) maintaining at normal pressure under the concentration.
Comparative example 4 is 1000g of steel slag and comparative example 2 is prepared by dissolving CO in advance by supercritical method 2 Mixing with water, demolding after 4 hr, and treating with 20% CO 2 And (5) maintaining at normal pressure under the concentration.
To illustrate the direct increase of CO in the mix water 2 Or CO 3 2- The influence of the concentration on the development of the cement strength of the carbonized steel slag is highlighted so as to promote the gas-phase CO by the technical scheme of the invention 2 Dissolution and inward diffusion, and the action mechanism of reducing the activation energy of the carbonization reaction. Comparative example 5 is a reaction of 1mol of Na 2 CO 3 Dissolving in 1L deionized water, standing, cooling to obtain water solution containing dissolved CO 2 About 44g, then mixing with 1000g of steel slag, and carrying out standard curing.
TABLE 5 compressive strength (MPa) at specific age of curing of carbide slag cement
| 1d strength | 3d strength | 7d strength | |
| Example 4 | 6.7 | 14.5 | 30.6 |
| Example 5 | 7.6 | 16.3 | 36.4 |
| Example 6 | 5.7 | 9.7 | 22.6 |
| Example 7 | 5.6 | 9.2 | 23.9 |
| Comparative example 3 | 3.2 | 4.6 | 7.2 |
| Comparative example 4 | 1.2 | 5.4 | 9.9 |
| Comparative example 5 | 1.0 | 3.9 | 5.3 |
In combination with the strength of 1d, 3d and 7d cured with the carbonized steel slag cements obtained in examples 4 to 7 and comparative examples 4 to 5 of Table 5, the proposed solution of the present invention based on CO 2 The strength promoter with improved solubility and diffusion rate can obviously increase the compressive strength of the carbonized steel slag cement. According to a comparison of FIGS. 1 and 2, the absence of CO in the solution according to the invention 2 Solubility and diffusion rate promoting agent conditionsThe carbonized steel slag contains a large amount of calcium hydroxide, namely, CO 2 The solubility was low, and the carbonization reaction could not be completed. When the accelerating agent of the scheme of the invention is added, the carbonization reaction is remarkably accelerated, the dicalcium silicate is greatly consumed, and the product is completely carbonized to generate calcium carbonate.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (8)
1. The cement strength improver for the carbonized steel slag is characterized by being a mixture of more than two of monoethanolamine, polyalcohol amine or N-methyl polyalcohol amine.
2. The carbonized steel slag cement strength improver as claimed in claim 1, wherein the polyalcohol amine is diethanolamine or triethanolamine, and the N-methyl polyalcohol amine is N-methyl diethanolamine.
3. The cement strength improver of carbonized steel slag cement as claimed in claim 2, wherein the mass ratio of diethanolamine to triethanolamine or diethanolamine to N-methyldiethanolamine is 2.5-1: 1.
4. The cement strength improver of carbonized steel slag as claimed in claim 1, wherein the grain size of the steel slag powder is less than 80 μm, and the specific surface area is more than 400m 2 /kg。
5. The carbonized steel slag cement strength improver as claimed in claim 1, wherein the elemental iron content of the steel slag powder is less than 10 wt%.
6. The application method of the carbonized steel slag cement strength improver as claimed in claim 1, which is characterized by comprising the following steps: mixing the carbonized steel slag cement strength improver with mixing water uniformly in advance to obtain an aqueous solution of the carbonized steel slag cement strength improver, standing, mixing with steel slag, removing a mold, and adopting CO 2 And (6) carbonizing and curing.
7. The use method of the steel carbide slag cement strength improver as claimed in claim 6, wherein the mass concentration of the aqueous solution of the steel carbide slag cement strength improver is 5-25%.
8. The use method of the steel slag carbide cement strength improver as claimed in claim 5, wherein the mass ratio of the steel slag to the steel slag carbide cement strength improver is 1000: 12-65.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115259737A (en) * | 2022-08-18 | 2022-11-01 | 青岛理工大学 | Titanium sol carbon-fixing auxiliary agent, preparation method and application thereof, and method for solidifying carbon by using cement-based material |
| CN115304314A (en) * | 2022-08-26 | 2022-11-08 | 武汉理工大学 | Carbon dioxide driven hardened ultra-high performance concrete and preparation method thereof |
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| CN113845317A (en) * | 2021-09-24 | 2021-12-28 | 广西源盛矿渣综合利用有限公司 | Clinker-free solid waste system cement and manufacturing method thereof |
| CN113979653A (en) * | 2021-12-01 | 2022-01-28 | 沈阳建筑大学 | Steel slag cementing material, preparation method and application |
| WO2022051598A2 (en) * | 2020-09-03 | 2022-03-10 | Cornell University | Methods and systems for producing solid inorganic carbonate and bicarbonate compounds |
| CN114290511A (en) * | 2021-12-23 | 2022-04-08 | 湖南大学 | Method for enhancing carbon dioxide solid existence in cement-based material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056202A (en) * | 2017-05-31 | 2017-08-18 | 盐城工学院 | Carbonization slag cement prepares accelerator and its application process of low-carbon binder materials |
| WO2022051598A2 (en) * | 2020-09-03 | 2022-03-10 | Cornell University | Methods and systems for producing solid inorganic carbonate and bicarbonate compounds |
| CN113845317A (en) * | 2021-09-24 | 2021-12-28 | 广西源盛矿渣综合利用有限公司 | Clinker-free solid waste system cement and manufacturing method thereof |
| CN113979653A (en) * | 2021-12-01 | 2022-01-28 | 沈阳建筑大学 | Steel slag cementing material, preparation method and application |
| CN114290511A (en) * | 2021-12-23 | 2022-04-08 | 湖南大学 | Method for enhancing carbon dioxide solid existence in cement-based material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115259737A (en) * | 2022-08-18 | 2022-11-01 | 青岛理工大学 | Titanium sol carbon-fixing auxiliary agent, preparation method and application thereof, and method for solidifying carbon by using cement-based material |
| CN115304314A (en) * | 2022-08-26 | 2022-11-08 | 武汉理工大学 | Carbon dioxide driven hardened ultra-high performance concrete and preparation method thereof |
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