CN112430051A - Building material prepared by synergistic carbonization of steel slag, desulfurized gypsum and fly ash and method - Google Patents
Building material prepared by synergistic carbonization of steel slag, desulfurized gypsum and fly ash and method Download PDFInfo
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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
- C04B28/14—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 calcium sulfate cements
- C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/144—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
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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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Abstract
The invention belongs to the field of solid waste building materials, and particularly relates to a building material prepared by synergistic carbonization of steel slag-desulfurized gypsum-fly ash and a method, which is prepared from the following raw materials and processes: the raw materials comprise steel slag, desulfurized gypsum, fly ash, sodium carbonate, ammonium bicarbonate, fine aggregate, coarse aggregate, retarder, water reducing agent and defoaming agent, the raw materials are added with water, stirred, vibrated or pressed to form, then the mold is removed for 2-4 h, a test piece is placed in a reaction kettle, and the temperature, the humidity, the pressure and the CO of the reaction kettle are controlled2And (3) carrying out low-temperature and high-temperature two-stage carbonization curing to obtain the building material according to the volume concentration. The invention utilizes the carbonization excitant to promote the cooperative carbonization of the steel slag, the desulfurized gypsum and the fly ash, improves the carbonization conversion rate and efficiency, and realizes the solid waste resource utilization of the steel slag, the desulfurized gypsum and the fly ash and the capture of CO in industrial waste gas2Provides an effective method for preparing building materials.
Description
Technical Field
The invention belongs to the field of solid waste building materials, and particularly relates to a building material prepared by synergistic carbonization of steel slag-desulfurized gypsum-fly ash and a method.
Background
With the development of the steel industry in China, the yield of the steel slag is rapidly increased. The large amount of steel slag is piled up, which not only wastes resources, but also brings great pollution to the environment. The steel slag has certain gelling activity and can be used as low-grade cement, but the free CaO and free MgO in the steel slag are high in content, so that the stability problem of a gelled material prepared from the steel slag occurs. In general, the resource utilization rate of the steel slag in China is low.
Fly ash has large differences in properties depending on the combustion technology. The common fly ash formed by burning the common fly ash furnace has high activity and can be widely applied to cement concrete products. However, the fly ash discharged by the circulating fluidized bed boiler is obviously different from the common fly ash in chemical composition and micro-morphology. The circulating fluidized bed boiler adopts in-furnace desulfurization to produce powdered coalThe ash is commonly referred to as sulfur fixation ash. The sulfur-fixing ash is rich in free CaO and CaSO of calcareous sulfur-fixing components4The application of the cement-based material is easy to cause expansion cracking. And the loose porous microstructure and high carbon content of the sulfur-fixing ash lead to an increase in water demand for use in cement-based materials, thereby reducing material strength. Therefore, the fluidized bed combustion ash slag is difficult to be applied to cement-based materials, and the resource utilization of the fluidized bed combustion ash slag is limited.
In addition, with the improvement of environmental protection on desulfurization requirements, the annual output of the desulfurized gypsum is gradually increased, and the resource utilization of the gypsum is also in need.
CO2To be a greenhouse gas, a promising mode of emission reduction is carbon capture and sequestration. The safest method is based on CO2React with calcium or magnesium oxides or hydroxides to form stable, industrially desirable carbonate materials.
Based on this, steel slags, desulfurized gypsum, fly ash, in particular solid sulfur ash, are rich in calcareous materials such as free CaO, free MgO, CaSO4For capturing and fixing CO2The formation of carbonate cements offers the possibility. The carbon-fixing function of the steel slag, the desulfurized gypsum and the fly ash is utilized to prepare the building material, so that an effective way is provided for the resource utilization of the steel slag, the desulfurized gypsum and the fly ash.
The patent application of a method for preparing carbonized building materials by using steel slag tail mud (application No. 201910055376.5), a method for preparing light carbonized building materials by using steel slag (application No. 201910054715.8), a method for efficiently preparing low-cost carbonized bricks by using steel slag (application No. 201910054720.9), and a method for preparing high-strength carbonized building materials by using steel slag micro powder (application No. 201910054726.6) disclose a method for preparing carbonized building materials by using steel slag, steel slag tail mud and steel slag micro powder, combining desulfurized gypsum or natural gypsum and adding fine aggregates and light aggregates. The four patents take the steel slag and the desulfurized gypsum or the natural gypsum as main carbonization reaction raw materials, and the normal-pressure carbonization box is adopted for carbonization and maintenance, so that the defects of long carbonization and maintenance time, small carbon fixation amount, low carbonization conversion rate of calcium materials in solid wastes and the like exist, and the carbonization and maintenance strength can reach more than 15-50 MPa within several days.
The invention adds fly ash, especially solid sulfur ash with high calcium content, in cooperation with steel slag and desulfurized gypsum, and adds carbonization excitant sodium carbonate and ammonium bicarbonate, and adopts two-stage continuous carbonization, so that not only oxides such as free Ca and the like can be carbonized, but also calcium-containing amorphous phases in the steel slag and the fly ash can participate in carbonization reaction, and the strength of the steel slag and the fly ash can reach more than 50MPa within several hours.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the building material prepared by the steel slag-desulfurized gypsum-fly ash through the synergic carbonization and the method. Solid waste resource utilization of steel slag, desulfurized gypsum and fly ash and industrial waste gas CO capture2The prepared building material can be widely applied to the preparation and production of green solid waste buildings.
In order to achieve the purpose, the invention adopts the following technical scheme:
the building material prepared by the synergistic carbonization of the steel slag, the desulfurized gypsum and the fly ash comprises the following raw materials in parts by weight:
30-60 parts of steel slag, 20-40 parts of desulfurized gypsum, 10-15 parts of fly ash, 0.5-2 parts of sodium carbonate, 0.1-0.3 part of ammonium bicarbonate, 0-100 parts of fine aggregate, 0-150 parts of coarse aggregate, 0.05-0.08 part of retarder, 0.1-0.5 part of water reducer and 0.1-0.3 part of defoaming agent.
Further, the fly ash is one or a mixture of several of common fly ash, solid sulfur ash and denitration fly ash produced by a pulverized coal furnace according to any proportion. The volcanic ash activity of the common fly ash, the solid sulfur ash or the denitration fly ash is excited in the alkaline environment of the steel slag to provide larger early strength, most importantly, the calcium component contained in the common fly ash, the solid sulfur ash or the denitration fly ash can improve the later strength of the material under the excitation of carbonization, and especially, the calcium-containing amorphous phase contained in the common fly ash, the solid sulfur ash or the denitration fly ash can improve the strength of the material in the high-temperature carbonization stage.
Further, the particle size of the fine aggregate is 0.075 mm-4.75 mm, and the packageThe fine aggregate is obtained by mixing and grading one or more of fine aggregate crushed and sieved by construction waste and sand crushed and sieved by coal gangue solid waste, wherein the fine aggregate comprises sand, recycled sand and the like, or the fine aggregate is the fine aggregate with the bulk density of less than 1200kg/m3The light fine aggregate comprises one or a mixture of several of expanded perlite, vitrified micro bubbles, expanded vermiculite and polyphenyl granules which are mixed according to any proportion. The strength of the material can be obviously improved by adding common fine aggregate such as sand and the like, the material is used for preparing the steel slag-desulfurized gypsum-fly ash synergic carbonization load-bearing building material, the heat insulation performance of the material is improved by reducing the weight of the material by adopting the light fine aggregate, and the material can be used for preparing the steel slag-desulfurized gypsum-fly ash synergic carbonization heat insulation building material with good heat insulation performance.
Further, the particle size of the coarse aggregate is more than 4.75mm, the coarse aggregate is obtained by mixing and grading one or more of coarse aggregate obtained by crushing and screening construction waste such as carpolite, regenerated carpolite and the like and sand obtained by crushing and screening coal gangue solid waste, or the coarse aggregate is the coarse aggregate with the stacking density of less than 1100kg/m3The light coarse aggregate comprises one or a mixture of a plurality of ceramsite, pumice and spontaneous combustion coal gangue which are mixed according to any proportion. The addition of coarse aggregate such as pebbles, regenerated pebbles and the like can obviously improve the strength of the material, and is used for preparing the steel slag-desulfurized gypsum-fly ash synergic carbonization load-bearing building material, while the adoption of the light coarse aggregate can not only reduce the weight of the material but also improve the heat-insulating property of the material, and can be used for preparing the steel slag-desulfurized gypsum-fly ash synergic carbonization heat-insulating building material with good heat-insulating property and higher strength.
Further, the retarder is one of an organic acid retarder, a phosphate retarder and a protein retarder. The retarder can effectively solve the problem that the initial setting time is too short to influence the development of the subsequent process when the steel slag, the desulfurized gypsum, the fly ash and the water are mixed and stirred to prepare slurry, and simultaneously solves the problems of too low strength and the like caused by too short initial setting time.
Further, the water reducing agent is a polycarboxylic acid water reducing agent. The working performance of the slurry during preparation is improved by adding a proper amount of water reducing agent, the water consumption can be effectively reduced, and the appearance quality and the strength of the finally prepared material are obviously improved.
Further, the solid sulfur ash is the solid sulfur ash generated by the combustion of the circulating fluidized bed boiler. Free CaO and CaSO contained in the sulfur-fixing ash4Is much higher than common fly ash, is used as a calcium-rich solid waste, has limited application in cement concrete, but is rich in CaO and CaSO4Provides favorable conditions for preparing the carbonized building material. The carbonized building material is prepared by utilizing the sulfur fixation ash, and an effective way is provided for resource utilization of the sulfur fixation ash.
Further, the organic acid retarder is a citric acid retarder. The citric acid is a common organic acid and has the characteristics of low price and good retarding effect.
The method for preparing the building material by the synergistic carbonization of the steel slag, the desulfurized gypsum and the fly ash comprises the following steps:
(1) weighing steel slag, desulfurized gypsum, fly ash, sodium carbonate, ammonium bicarbonate, fine aggregate, coarse aggregate, retarder, water reducer and defoamer according to the weight parts of the raw materials;
(2) uniformly stirring water and the raw materials in the step (1) to obtain a mixture, putting the mixture into a mold, obtaining a molded test piece by adopting a vibration molding or compression molding process, placing the molded test piece in air at normal temperature and normal pressure, and removing the mold to obtain a test piece;
(3) placing the test piece obtained in the step (2) in CO2In the reaction kettle, controlling the CO2Temperature, relative humidity, CO in the reaction kettle2Volume concentration, CO2And gas pressure, and a carbonization curing method of low-temperature carbonization curing and high-temperature carbonization curing is adopted to obtain the building material prepared by the synergistic carbonization of the steel slag, the desulfurized gypsum and the fly ash. Reasonable control of CO2Temperature, relative humidity, CO in the reaction kettle2Volume concentration, CO2The gas pressure can fully carbonize calcium substances in the steel slag, the desulfurized gypsum and the fly ash at different stages to produce the calcium carbonate cementing material, and the physical and mechanical properties of the building material prepared by the synergistic carbonization of the steel slag, the desulfurized gypsum and the fly ash are obviously improved.
Further, the quality of the water in the step (2) is equal to that of the steel slag and the water is removedThe total mass ratio of the sulfur gypsum to the fly ash is 0.2-0.5: 1. The reasonable proportion can lead the steel slag, the desulfurized gypsum and the fly ash to work cooperatively and improve the fixed CO of the steel slag2And the performance of the building material is finally improved, so that the building material has higher strength.
Further, the pressure of the compression molding in the step (2) is 20-30 MPa. The reasonable forming pressure can not only ensure that the building material has good strength performance, but also reduce the preparation cost.
Further, the time for placing the formed test piece in the step (2) in the air at normal temperature and normal pressure is 2-4 h. By adding the retarder, the final setting and demolding time in the preparation process is controlled to be 2-4 h, the preparation efficiency of the material can be remarkably improved, and the preparation cost is further reduced.
Further, the carbonization and maintenance method in the two stages of low-temperature carbonization and high-temperature carbonization and maintenance in the step (3) specifically includes: firstly, in the low-temperature carbonization curing stage, the CO is added2The temperature in the reaction kettle is controlled to be 5-40 ℃, the relative humidity is controlled to be 80-90 percent, and the CO is added2Introducing CO into the reaction kettle2And air, said CO2The volume concentration of the CO is 0.03-20 percent, and the CO is2Controlling the pressure of the reaction kettle to be 0.1-0.4 MPa, and carrying out carbonization reaction for 20-90 min; after the low-temperature carbonization curing stage is finished, starting the high-temperature carbonization curing stage, and introducing the CO2The temperature of the reaction kettle is increased, the temperature is controlled to be 140-230 ℃, the relative humidity is controlled to be 80-90 percent, and the reaction kettle is continuously heated to the CO2Introducing CO into the reaction kettle2And air, said CO2The volume concentration of (A) is 20-60%, and the CO is2The pressure of the reaction kettle is increased to 0.5-1.0 MPa, and the carbonization reaction is carried out for 2-6 h. Rational and accurate control of CO2Temperature, relative humidity, CO in the reaction kettle2Volume concentration, CO2The gas pressure and the carbonization time can realize the carbonization curing method with two stages of low-temperature carbonization curing and high-temperature carbonization curing. The two-stage carbonization curing method can better ensure that the prepared material has the acquireability in shorter time under more economic and effective preparation conditionsCan better cooperate with the carbonized building material of steel slag-desulfurized gypsum-fly ash. The low-temperature carbonization curing stage can quickly carbonize free calcium such as CaO in the steel slag, the desulfurized gypsum and the fly ash and enable the material to have higher initial strength, and the high-temperature carbonization curing stage can further carbonize a calcium-containing amorphous phase on the basis of hydration reaction and further improve the strength of the material, and if CO is adopted, CO-containing amorphous phase2The two-stage carbonization curing process of the industrial waste gas can obviously absorb CO in the industrial waste gas2Obviously improve the fixed CO of the steel slag-desulfurized gypsum-fly ash cooperated with the carbonized building material2And the environment-friendly characteristic of the invention is reflected.
Further, the CO is2Can be prepared from a mixture containing CO2Of air or containing CO2Industrial waste gas replacement.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention fully utilizes Ca sources and metal oxides which are rich in solid wastes such as steel slag, desulfurized gypsum, fly ash and the like to produce carbonate cementing materials which take calcium carbonate as a main component through carbonization reaction to prepare building materials, and provides an effective way for resource utilization and cooperative disposal of a large amount of solid waste steel slag, desulfurized gypsum, fly ash and the like.
2. The steel slag-desulfurized gypsum-fly ash are adopted to work cooperatively, the desulfurized gypsum can promote the carbonization of the steel slag, the pH value of a liquid phase in the composite material is further improved by adding the fly ash, the hydration reaction of active ingredients of the steel slag is promoted, and the carbonization reaction activity of the steel slag and the desulfurized gypsum is improved.
3. The invention adopts sodium carbonate and ammonium bicarbonate as the carbonization reaction excitant, obviously improves the respective carbonization rates of the steel slag, the desulfurized gypsum and the fly ash, and improves the performance of preparing the building material by carbonization. Firstly, sodium carbonate and ammonium bicarbonate enter a material liquid phase to improve the alkalinity and increase the hydration reaction of the steel slag; secondly, CO produced by the dissolution of sodium carbonate and ammonium bicarbonate3 2-Increase CO in the liquid phase of the material3 2Saturation degree, and increased Ca in steel slag, desulfurized gypsum and fly ash2+Formation of CaCO3The efficiency of (c); then, the product is processedSecond, NH produced by decomposition of ammonium bicarbonate4 +The alkalinity of the liquid phase in the material is improved, and the absorption of CO by the material is further accelerated2And converted into CO3 2-Thereby improving the carbonization efficiency; and finally, in the high-temperature carbonization curing stage, the sodium carbonate and the ammonium bicarbonate can promote calcium-containing amorphous phases in the steel slag and the fly ash to participate in carbonization reaction, so that the strength of the material is further improved.
4. The steel slag-desulfurized gypsum-fly ash is adopted to prepare the building material by the synergistic carbonization, so that the efficiency of the carbonization reaction of the material is obviously improved, and the fixation and the paving of CO in the material are increased2For reducing CO in industrial waste gas2Emission and CO of2The in situ fixation of (a) provides a method.
5. The invention has high utilization rate of solid waste, and the prepared building material has good performance, and can be applied to trapping CO in industrial waste gas2The method has the characteristic of green building material preparation in the field of synergistic building material preparation.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The building material prepared by the synergistic carbonization of the steel slag, the desulfurized gypsum and the fly ash comprises the following raw materials in parts by weight: 30-60 parts of steel slag, 20-40 parts of desulfurized gypsum, 10-15 parts of fly ash, 0.5-2 parts of sodium carbonate, 0.1-0.3 part of ammonium bicarbonate, 0-100 parts of fine aggregate, 0-150 parts of coarse aggregate, 0.05-0.08 part of retarder, 0.1-0.5 part of water reducer and 0.1-0.3 part of defoaming agent.
The coal ash is a mixture of one or more of common coal ash, solid sulfur ash and denitration coal ash which are generated by a coal powder furnace and mixed according to any proportion, and the solid sulfur ash is solid sulfur ash generated by burning a circulating fluidized bed boiler; the particle size of the fine aggregate is 0.075 mm-4.75 mm, the fine aggregate comprises one or more of fine aggregate crushed and sieved by construction waste and sand crushed and sieved by coal gangue solid waste, and is obtained by mixing and grading, or the fine aggregate is the fine aggregate with the bulk density less than 1200kg/m3The light fine aggregate comprises one or more of expanded perlite, vitrified micro-beads, expanded vermiculite and polyphenyl granules according to any proportion(ii) the mixed mixture; the particle size of the coarse aggregate is more than 4.75mm, the coarse aggregate is obtained by mixing and grading one or more of coarse aggregate crushed and sieved by construction waste and sand crushed and sieved by coal gangue solid waste, or the coarse aggregate is the coarse aggregate with the bulk density less than 1100kg/m3The light coarse aggregate comprises one or a mixture of a plurality of ceramsite, pumice and spontaneous combustion coal gangue which are mixed according to any proportion; the retarder is one of an organic acid retarder, a phosphate retarder and a protein retarder, and the organic acid retarder is a citric acid retarder; the water reducing agent is a polycarboxylic acid water reducing agent.
A method for preparing a building material by synergistic carbonization of steel slag-desulfurized gypsum-fly ash comprises the following steps:
(1) weighing steel slag, desulfurized gypsum, fly ash, sodium carbonate, ammonium bicarbonate, fine aggregate, coarse aggregate, retarder, water reducer and defoamer according to the weight parts of the raw materials;
(2) uniformly stirring water and the raw materials in the step (1) to obtain a mixture, wherein the ratio of the mass of the water to the total mass of the steel slag, the desulfurized gypsum and the fly ash is 0.2-0.5: 1; putting the mixture into a mold, and obtaining a molded test piece by adopting a vibration molding or compression molding process, wherein the pressure of compression molding is 20-30 MPa; and (3) placing the molded test piece in the air at normal temperature and normal pressure for 2-4 h, and then removing the mold to obtain the test piece.
(3) Placing the test piece obtained in the step (2) in CO2In the reaction kettle, controlling the CO2Temperature, relative humidity, CO in the reaction kettle2Volume concentration, CO2The method comprises the following steps of gas pressure and carbonization time, and adopts a carbonization curing method with two stages of low-temperature carbonization curing and high-temperature carbonization curing, and specifically comprises the following steps: firstly, in the low-temperature carbonization curing stage, the CO is added2The temperature in the reaction kettle is controlled to be 5-40 ℃, the relative humidity is controlled to be 80-90 percent, and the CO is added2Introducing CO into the reaction kettle2And air, said CO2Can be prepared from a mixture containing CO2Of air or containing CO2Industrial waste gas replacement of, said CO2The volume concentration of the CO is 0.03-20 percent, and the CO is2Reaction ofControlling the pressure of the kettle at 0.1-0.4 MPa, and carrying out carbonization reaction for 20-90 min; after the low-temperature carbonization curing stage is finished, starting the high-temperature carbonization curing stage, and introducing the CO2The temperature of the reaction kettle is increased, the temperature is controlled to be 140-230 ℃, the relative humidity is controlled to be 80-90 percent, and the reaction kettle is continuously heated to the CO2Introducing CO into the reaction kettle2And air, said CO2The volume concentration of (A) is 20-60%, and the CO is2And raising the pressure of the reaction kettle to 0.5-1.0 MPa, and carrying out carbonization reaction for 2-6 h to finally obtain the building material prepared by the synergistic carbonization of the steel slag, the desulfurized gypsum and the fly ash.
The method comprises the following specific implementation steps:
(1) weighing the raw materials in parts by weight shown in Table 1;
(2) the mass of water was calculated according to the W/b in Table 1 (note: the W/b in Table 1 is the ratio of the mass W of water to the total mass b of the three materials, steel slag, desulfurized gypsum and fly ash, and the mass of water was calculated based on this ratio), and the water was weighed according to this mass. Then putting water and the raw materials weighed in the step (1) into a stirrer to be uniformly stirred to obtain a mixture; then, the mixture is put into a die, and a test piece is formed according to the forming process corresponding to the table 2; then placing the molded test piece in the air at normal temperature and normal pressure for 2-4 h, and removing the mold to obtain a test piece;
(3) placing the test piece obtained in the step (2) in CO2Carrying out carbonization reaction in the reaction kettle. Specifically, the two-stage carbonization curing method of low-temperature carbonization curing and high-temperature carbonization curing is performed as shown in table 2. Wherein, the low-temperature carbonization maintenance is performed according to the following table 2, and CO is firstly controlled2The temperature in the reaction kettle reaches C1, CO2Controlling the relative humidity in the reaction kettle at H1, and then feeding CO2Introducing CO into the reaction kettle2And air mixed gas of CO2Volume concentration of V1, and control of CO2The pressure of the reaction kettle is S1, and the carbonization reaction time is T1. After the low-temperature carbonization is finished, the carbonization and maintenance at the high-temperature stage is started, namely CO2The reactor was brought to a temperature of C2, humidity controlled at H2, aerated and CO allowed to flow2Volume concentration of V2, and CO2The pressure of the reaction kettle reaches S2, and the carbonization reaction is T2.
TABLE 1 parts by weight of the raw materials for the examples
Table 2 examples of the forming process
| Example numbering | Molding process | Pressure of formation | Time to demold |
| Example 1 | Vibration forming | - | 4h |
| Example 2 | Vibration forming | - | 4h |
| Example 3 | Vibration forming | - | 4h |
| Example 4 | Vibration forming | - | 4h |
| Example 5 | Vibration forming | - | 2.5h |
| Example 6 | Press forming | 20MPa | 2h |
| Example 7 | Vibration forming | - | 3h |
| Example 8 | Vibration forming | - | 3h |
| Example 9 | Vibration forming | - | 2h |
| Example 10 | Vibration forming | - | 2h |
| Example 11 | Vibration forming | - | 2h |
| Example 12 | Press forming | 20MPa | 2h |
| Example 13 | Press forming | 25MPa | 2h |
| Example 14 | Press forming | 30MPa | 2h |
TABLE 3 carbonization Process and corresponding compressive Strength for the examples
(4) As shown in Table 3, the compressive strength of the building materials prepared by the synergistic carbonization of the steel slag-desulfurized gypsum-fly ash is obtained for each example. Example 2 the building material prepared by using the sulfur-fixing ash in comparison with the common fly ash in example 1 has higher strength. However, as can be seen from examples 2 and 3, the addition of carbonation activators sodium carbonate and ammonium bicarbonate can improve the final strength of the material. Comparing examples 2 and 4, it is known that increasing the temperature of the reaction vessel can shorten the carbonization time and obtain a material with higher strength. From examples 4 and 5, it is understood that the strength of the material can be improved by increasing the content of desulfurized gypsum having a high calcium content. It is clear from examples 5 and 6 that the final strength of the material can be increased by using a press-forming process. From examples 7, 8 and 9, it is understood that although the amounts of desulfurized gypsum and sulfur-fixing ash are reduced, the strength of the material can be improved by increasing the amount of sand and stones in the aggregate. From example 10, it can be seen that the strength of the material can be further improved by decreasing the ratio of the mass of water to the total mass of the three materials, i.e., W/b, of the steel slag, desulfurized gypsum and fly ash. From example 11, it can be known that the material with the strength of 51.8MPa can be prepared by optimizing the proportion and the process of each material, and from example 12, the strength of the material is further improved by adopting the compression molding, and the compressive strength reaches 58.3 MPa. As is clear from comparison of examples 12, 13 and 14, the strength of the material can be improved by increasing the molding pressure, and the compressive strength reaches 68.7MPa when the molding pressure for press molding is 30 MPa.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the detailed description is made with reference to the embodiments of the present invention, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which shall be covered by the claims.
Claims (10)
1. The building material prepared by the synergistic carbonization of the steel slag, the desulfurized gypsum and the fly ash is characterized in that: the building material prepared by the steel slag-desulfurized gypsum-fly ash through synergic carbonization comprises the following raw materials in parts by weight:
30-60 parts of steel slag, 20-40 parts of desulfurized gypsum, 10-15 parts of fly ash, 0.5-2 parts of sodium carbonate, 0.1-0.3 part of ammonium bicarbonate, 0-100 parts of fine aggregate, 0-150 parts of coarse aggregate, 0.05-0.08 part of retarder, 0.1-0.5 part of water reducer and 0.1-0.3 part of defoaming agent.
2. The steel slag-desulfurized gypsum-fly ash synergic-carbonization prepared building material according to claim 1, characterized in that: the fly ash is one or a mixture of a plurality of common fly ash, sulfur fixation ash and denitration fly ash which are produced by a fly ash furnace and are mixed according to any proportion;
the particle size of the fine aggregate is 0.075 mm-4.75 mm, and the fine aggregate comprises one or more of fine aggregate crushed and sieved by construction waste and sand crushed and sieved by coal gangue solid wasteFine aggregate obtained by grading, or the fine aggregate has a bulk density less than 1200kg/m3The light fine aggregate comprises one or a mixture of several of expanded perlite, vitrified micro bubbles, expanded vermiculite and polyphenyl granules which are mixed according to any proportion;
the particle size of the coarse aggregate is more than 4.75mm, the coarse aggregate is obtained by mixing and grading one or more of coarse aggregate crushed and sieved by construction waste and sand crushed and sieved by coal gangue solid waste, or the coarse aggregate is the coarse aggregate with the bulk density less than 1100kg/m3The light coarse aggregate comprises one or a mixture of a plurality of ceramsite, pumice and spontaneous combustion coal gangue which are mixed according to any proportion;
the retarder is one of an organic acid retarder, a phosphate retarder and a protein retarder;
the water reducing agent is a polycarboxylic acid water reducing agent.
3. The steel slag-desulfurized gypsum-fly ash synergic-carbonization prepared building material according to claim 2, characterized in that: the solid sulfur ash is produced by burning a circulating fluidized bed boiler.
4. The steel slag-desulfurized gypsum-fly ash synergic-carbonization prepared building material according to claim 2, characterized in that: the organic acid retarder is a citric acid retarder.
5. The method for preparing the building material by the synergistic carbonization of the steel slag, the desulfurized gypsum and the fly ash is characterized by comprising the following steps of: the method comprises the following steps:
(1) weighing steel slag, desulfurized gypsum, fly ash, sodium carbonate, ammonium bicarbonate, fine aggregate, coarse aggregate, retarder, water reducer and defoamer according to the weight parts of the raw materials;
(2) uniformly stirring water and the raw materials in the step (1) to obtain a mixture, putting the mixture into a mold, obtaining a molded test piece by adopting a vibration molding or compression molding process, placing the molded test piece in air at normal temperature and normal pressure, and removing the mold to obtain a test piece;
(3) placing the test piece obtained in the step (2) in CO2In the reaction kettle, controlling the CO2Temperature, relative humidity, CO in the reaction kettle2Volume concentration, CO2Gas pressure and carbonization time, and adopting a carbonization curing method with two stages of low-temperature carbonization curing and high-temperature carbonization curing to obtain the building material prepared by the synergic carbonization of the steel slag, the desulfurized gypsum and the fly ash.
6. The method for preparing the building material by the synergic carbonization of the steel slag, the desulfurized gypsum and the fly ash as claimed in claim 5, is characterized in that: the ratio of the mass of the water in the step (2) to the total mass of the steel slag, the desulfurized gypsum and the fly ash is 0.2-0.5: 1.
7. The method for preparing the building material by the synergic carbonization of the steel slag, the desulfurized gypsum and the fly ash as claimed in claim 5, is characterized in that: and (3) the pressure of the compression molding in the step (2) is 20-30 MPa.
8. The method for preparing the building material by the synergic carbonization of the steel slag, the desulfurized gypsum and the fly ash as claimed in claim 5, is characterized in that: the standing time in the step (2) is 2-4 h.
9. The method for preparing the building material by the synergic carbonization of the steel slag, the desulfurized gypsum and the fly ash as claimed in claim 5, is characterized in that: the carbonization and maintenance method in the two stages of low-temperature carbonization and maintenance and high-temperature carbonization and maintenance in the step (3) specifically comprises the following steps:
firstly, in the low-temperature carbonization curing stage, the CO is added2The temperature in the reaction kettle is controlled to be 5-40 ℃, the relative humidity is controlled to be 80-90 percent, and the CO is added2Introducing CO into the reaction kettle2And air, said CO2The volume concentration of the CO is 0.03-20 percent, and the CO is2Controlling the pressure of the reaction kettle to be 0.1-0.4 MPa, and carrying out carbonization reaction for 20-90 min; after the low-temperature carbonization curing stage is finished, starting the high-temperature carbonization curing stage, and introducing the CO2The temperature of the reaction kettle is increased, the temperature is controlled to be 140-230 ℃, the relative humidity is controlled to be 80-90 percent, and the reaction kettle is continuously heated to the CO2Introducing CO into the reaction kettle2And air, said CO2The volume concentration of (A) is 20-60%, and the CO is2The pressure of the reaction kettle is increased to 0.5-1.0 MPa, and the carbonization reaction is carried out for 2-6 h.
10. The method for preparing the building material by the synergic carbonization of the steel slag, the desulfurized gypsum and the fly ash as claimed in claim 9, is characterized in that: the CO is2Can be prepared from a mixture containing CO2Of air or containing CO2Industrial waste gas replacement.
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