CN115321897A - Low-carbon cementing material with high early strength and processing method thereof - Google Patents
Low-carbon cementing material with high early strength and processing method thereof Download PDFInfo
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- CN115321897A CN115321897A CN202210312025.XA CN202210312025A CN115321897A CN 115321897 A CN115321897 A CN 115321897A CN 202210312025 A CN202210312025 A CN 202210312025A CN 115321897 A CN115321897 A CN 115321897A
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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
- C04B28/04—Portland cements
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- 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
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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
- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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Abstract
The invention discloses a low-carbon cementing material with high early strength and a processing method thereof, belonging to the technical field of cementing materials. According to the invention, the lead smelting water coarse slag micro powder, calcium-based solid waste, magnesium-based solid waste, portland cement, slag micro powder and water are prepared into low-carbon cementing material slurry according to a certain proportion, and finally the low-carbon cementing material slurry is placed in a mold for solidification and molding and is subjected to microwave curing, steam oxygen protection and solidification treatment, so that the low-carbon cementing material with high strength is obtained. The low-carbon cementing material has low cost and realizes the resource utilization of solid wastes. The low-carbon cementing material prepared by the invention has a short preparation period, the compressive strength can reach 46.6MPa, and the low-carbon cementing material can be used for greatly replacing cement in the engineering fields of prefabricated parts of fabricated buildings, road construction and the like, has good economic and environmental benefits, and realizes the aim of assisting in double carbon.
Description
Technical Field
The invention belongs to the technical field of cementing materials, and particularly relates to a low-carbon cementing material with high early strength and a processing method thereof.
Background
The cement is the most widely used cementing material, and the cement yield in 2021 year is 23.63 hundred million tons in China, which is the first in the world. However, cement is also an industry with high pollution, high energy consumption and high emission, and the preparation process of the cement, namely 'two-grinding and one-burning', not only consumes a large amount of mineral resources such as calcium, siliceous materials, aluminum, iron and the like, but also consumes a large amount of energy, and discharges a large amount of carbon dioxide gas, other waste gases, waste water and the like. According to statistics, 1.6 to 1.7 tons of raw materials are consumed for producing one ton of cement clinker, 105 to 115kg of standard coal is consumed, and about 1 ton of CO is discharged 2 Greenhouse gases, while producing large amounts of nitrogen oxides, sulfur dioxide and dust. Aiming at the problems, the production of clinker-free or clinker-less low-carbon cementing materials which can replace cement is urgently needed.
Meanwhile, millions of tons of industrial byproducts, namely lead smelting water quenching waste residues, are generated every year due to the rapid development of lead smelting enterprises. According to statistics, when the lead smelting system produces 1 ton of lead and discharges 0.71 ton of lead smelting water quenching waste slag, the lead smelting waste slag has the characteristics of large yield, large increment, large stock quantity and low resource utilization. The open-air storage amount of the lead smelting waste residue is large, a large amount of land is occupied, the ecological environment is polluted and destroyed, the water source heavy metal pollution, the mining area soil heavy metal pollution and the mining area atmosphere pollution are caused, various geological disasters can be caused, the potential safety hazard exists, and the environment is greatly harmed. Although the lead smelting industry makes great contribution to the development and civilization progress of the human society, the environmental pollution caused by the lead smelting industry seriously affects the health and survival of human beings. Therefore, the severe problem of lead smelting water-quenched slag accumulation needs to be solved, and waste slag resources are utilized to the maximum extent.
Researches show that the lead smelting water-quenched slag is a glassy granular material with potential activity formed by high-temperature melting and water quenching, the glassy granular material is ground and mixed, and the potential hydration gelling performance of the glassy granular material can be excited by adding an alkaline solid waste activator (calcium-based solid waste, magnesium-based solid waste and slag micro powder), so that the utilization rate of the lead smelting slag can be improved, the environmental pollution is reduced, a low-carbon gelling material for replacing common portland cement can be obtained, and the low-carbon gelling material has good economic, social and environmental benefits.
Although the cementing material processed by utilizing various solid wastes has the advantage of low cost, compared with the traditional cement, the low-carbon cementing material still has the problems of slow hydration rate, long strength development period and low early strength.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a low-carbon cementing material with high early strength and a processing method thereof. The low-carbon cementing material is prepared by using lead smelting water-quenched slag and various solid wastes as raw materials, and the prepared low-carbon cementing material has the characteristics of high hydration speed, high early strength and low cost by adjusting the processing method.
The low-carbon cementing material with high early strength of the invention
The low-carbon cementing material with high early strength is characterized by comprising the following components in percentage by mass:
41.99 to 45.16 percent of lead smelting water quenching slag micro powder, 18.00 to 19.35 percent of calcium-based solid waste, 3.00 to 3.23 percent of magnesium-based solid waste, 19.35 to 25.01 percent of Portland cement, 12.00 to 12.90 percent of slag micro powder, and the sum of the mass percentages of the components is 100 percent.
Preferably, the lead smelting water-quenched slag micro powder is formed by shock-crushing non-ferrous lead and zinc smelting water-quenched slag into powder with the specific surface area of more than or equal to 350m 2 A/kg of micropowder.
Preferably, the calcium-based solid waste is lime-ash micropowder, wherein the CaO content is 45-55 wt%, and the specific surface area is more than or equal to 300m 2 /kg；
The magnesium-based solid waste is bischofite in a salt lake, and the specific surface area is more than or equal to 200m 2 /kg；
The 28-day strength of the Portland cement is more than or equal to 42.5MPa, and the specific surface area is more than or equal to 330m 2 /kg；
The slag micro powder is refinedThe specific surface area of the blast furnace slag micro powder generated by iron is more than or equal to 300m 2 And/kg, the 7d strength activity index of the slag micro powder is more than or equal to 55 percent, the 28d strength activity index is more than or equal to 75 percent, and the vitreous body content is more than or equal to 85 percent.
The invention also provides a processing method of the low-carbon cementing material with high early strength, which comprises the following specific steps:
(1) Drying, grinding and sieving lead smelting water-quenched slag at 105-110 ℃ to obtain lead smelting water-quenched slag with specific surface area of more than or equal to 350m 2 Per kg of lead smelting water quenching slag micro powder;
(2) Mixing the lead smelting water-quenched slag micro powder prepared in the step (1) with calcium-based solid waste, magnesium-based solid waste, portland cement, slag micro powder and water, and stirring for 5-7 min to prepare a cementing material slurry;
(3) Placing the prepared cementing material slurry in a mould, compacting, floating and forming;
(4) Putting the mold filled with the slurry into a microwave curing tank, and carrying out microwave curing at the curing temperature of 60-120 ℃, the microwave frequency of 2000MHZ and the curing time of 1-3.5 h;
(5) And (3) placing the mold after microwave curing into a curing box for steam curing, wherein the curing temperature is 40-80 ℃, and demolding is carried out after curing for 20.5-23 h, so as to obtain the low-carbon cementing material with high early strength.
Preferably, the mold is a Polyetheretherketone (PEEK) triple mold.
Preferably, in the step (4), water needs to be added into the mold during the microwave heating process so as to keep the relative humidity in the mold to be more than 95%.
Preferably, the microwave curing temperature of the step (4) is 100 ℃, and the curing time is 2.5h.
Preferably, the steam curing temperature in the step (5) is 80 ℃, and the curing time is 21.5h.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, by adjusting the raw material composition, the vitreous body activity in the lead smelting water-quenched slag micro powder is fully excited, so that the lead smelting water-quenched slag reacts with solid waste to generate a fibrous structure, the acting force between other solid waste and lead smelting water-quenched slag particles is improved, and the prepared low-carbon cementing material has a tighter structure and excellent compactness;
(2) The processing method of the low-carbon cementing material comprises the steps of firstly performing microwave curing and then performing steam curing. The microwave heating device has the advantages that the microwave heating device has deep action depth for heating objects, can realize synchronous temperature rise inside and outside the multi-solid waste low-carbon cementing material, avoids microstructure damage caused by stress difference caused by overhigh temperature difference inside and outside a test piece in the curing process, and can ensure that the test piece has strength reaching above the standard while realizing rapid curing. And then, the hydration reaction rate is further accelerated through steam curing, the hydration reaction degree is deepened, so that more water-soluble amorphous substances are formed, the early strength of the multi-solid waste low-carbon cementing material containing lead smelting water-quenched slag is improved, the curing period is shortened, and the energy consumption and pollution are reduced. Meanwhile, large-scale resource utilization of lead-zinc smelting waste slag is realized, the problem of pollution of lead smelting water-quenched slag to the environment is effectively solved, and the method has good environmental and economic benefits.
(3) The low-carbon cementing material prepared by the invention has the compressive strength of 46.6MPa, can be used in engineering fields such as prefabricated components and road construction, can obviously reduce the cement consumption, greatly reduce the carbon dioxide emission, reduce the cost, promote the resource utilization of solid wastes, has good environmental and economic benefits, and is convenient for large-scale popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of the strength of the low carbon cementitious material of the present invention;
FIG. 2 is an XRD diffraction pattern of the low-carbon cementing material prepared in the embodiment 1 of the invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
Example 1
A processing method of a low-carbon cementing material with high early strength comprises the following specific steps:
(1) Weighing 125.97g of lead smelting water-quenched slag micro powder, 54g of ash-melting slag, 9g of bischofite, 75.03g of cement and 36g of slag micro powder (namely blast furnace slag micro powder produced by iron making) according to the mass weight; additionally weighing 63.9g of water;
(2) Adding the lead smelting water-quenched slag micro powder, the melting ash, the bischofite silicate cement, the slag micro powder and water into a clean slurry stirring pot, and fully stirring for 5min to uniformly mix the materials to obtain a cementing material slurry;
(3) Pouring the low-carbon cementing material slurry prepared in the step (2) into a polyether ether ketone (PEEK) triple die with the thickness of 25mm multiplied by 25mm, fully inserting and tamping, compacting for 60s on a compaction table, and leveling the surface;
(4) Placing a sample into a microwave curing groove, inserting a heat conducting rod into the sample in the center for monitoring the temperature, setting curing temperature and temperature rising system by using a program, curing for 1h at the temperature of 60 ℃ in a microwave manner, supplementing water into the mold in the microwave heating process to keep the relative humidity in the mold to be more than 95%, wherein the microwave frequency is 2000MHZ;
(5) And (3) putting the sample subjected to microwave curing into a curing box for steam curing, setting the curing temperature to be 80 ℃, curing in the curing box for 23 hours, and then demolding to obtain the low-carbon cementing material with high early strength.
After microwave curing and steam curing, the XRD pattern of the 1-day hydration product of the sample is shown in fig. 2, and it can be seen from fig. 2 that the mineral phases in the 1-day hydration product of the low-carbon cementing material sample prepared in example 1 are mainly calcite, bischofite, hydroxycalcite, etc. and unreacted spodumene. The processing method can promote the release of the potential hydration activity of the lead smelting water-quenched slag, the hydration reaction is carried out, the hydrated gel which has great contribution to the product strength is formed, and the improvement of the mechanical property of the prepared gelled material is better realized.
Examples 2 to 4 and comparative examples 1 to 4
Examples 2 to 4 are the same as example 1 except that the microwave curing time in step (4) is different; comparative examples 1 to 4 are similar to example 1 except that the curing method in steps (4) and (5) is different, and are specifically shown in table 1:
table 1 maintenance mode comparison table
The compression strength of the test blocks of examples 1-4 and comparative examples 1-4 were then tested according to the Standard (GB/T17671-1999 "Cement mortar Strength test method (ISO method)). The results are shown in Table 2.
TABLE 2 compressive strength at different curing ages
As can be seen from the data in Table 2, the invention fully excites the gelling activity of the lead-zinc slag by adjusting the multi-solid waste components to generate a spatial three-dimensional network structure of the silicon-aluminum-calcium gel, so that the low-carbon gelling material has a compact overall structure and generates a certain strength.
Meanwhile, the microwave and steam curing mode is adopted for curing, so that the compressive strength of the test piece is obviously improved. When the test piece is cured for 1 day, the test piece is cured by adopting a microwave and curing combined curing mode in the examples 1 to 4, the compressive strength of the test piece is obviously higher than that of the test piece cured only by adopting steam curing in the comparative example, and the compressive strength of the standard cured test piece in the comparative example is the lowest compressive strength in 1 day. The compressive strength of the test piece subjected to steam curing for 3 days at the temperature of 80 ℃ is equal to that of the test piece subjected to curing for 1 day in the example 2-4; the strength of the test piece subjected to standard curing for 7 days still does not reach the compressive strength of the test piece subjected to curing for 1 day in examples 1 to 4. The method has the advantages that the microwave and steam curing mode is adopted, so that the synchronous heating of the inside and the outside of the multi-solid waste low-carbon cementing material can be realized, the microstructure damage caused by the stress difference caused by the overhigh temperature difference between the inside and the outside of a test piece in the curing process is avoided, the early strength of the multi-solid waste low-carbon cementing material containing lead smelting water-quenched slag is improved while the quick curing is realized, the curing period is shortened, and the energy consumption and the pollution are reduced.
The above description is only for the preferred embodiment of the present invention, and the protection scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention, the technical solution and the inventive concept of the present invention equivalent or change within the technical scope of the present invention.
Claims (8)
1. The low-carbon cementing material with high early strength is characterized by comprising the following components in percentage by mass:
41.99 to 45.16 percent of lead smelting water quenching slag micro powder, 18.00 to 19.35 percent of calcium-based solid waste, 3.00 to 3.23 percent of magnesium-based solid waste, 19.35 to 25.01 percent of Portland cement, 12.00 to 12.90 percent of slag micro powder, and the sum of the mass percentages of the components is 100 percent.
2. The low-carbon cementing material with high early strength as claimed in claim 1, wherein the micro powder of lead smelting water-quenched slag is formed by the shock pulverization of non-ferrous lead-zinc smelting water-quenched slag with a specific surface area of more than or equal to 350m 2 A/kg of micropowder.
3. The low-carbon cementing material with high early strength as claimed in claim 1, wherein said calcium-based solid wastes are lime-ash micropowder, in which CaO content is 45-55 wt%, specific surface area is more than or equal to 300m 2 /kg；
The magnesium-based solid waste is bischofite in a salt lake, and the specific surface area is more than or equal to 200m 2 /kg；
The 28-day strength of the portland cement is more than or equal to 42.5MPa, and the specific surface area is more than or equal to 330m 2 /kg；
The slag micro powder is blast furnace slag micro powder produced in iron making, and the specific surface area is more than or equal to 300m 2 Kg, the vitreous body content is more than or equal to 85wt percent.
4. The method for processing the low-carbon cementing material with high early strength according to any one of the claims 1 to 3, is characterized by comprising the following steps:
(1) Smelting leadDrying the water-quenched slag at 105-110 ℃, grinding and sieving to obtain the water-quenched slag with the specific surface area of more than or equal to 350m 2 Per kg of lead smelting water quenching slag micro powder;
(2) Mixing the lead smelting water quenching slag micro powder prepared in the step (1) with calcium-based solid waste, magnesium-based solid waste, portland cement, slag micro powder and water, and stirring for 5-7 min to prepare a cementing material slurry;
(3) Placing the prepared gelled material slurry in a mould, compacting and trowelling the slurry, and then forming the slurry;
(4) Placing the mold filled with the slurry into a microwave curing tank, and carrying out microwave curing at the curing temperature of 60-120 ℃, the microwave frequency of 2000MHZ and the curing time of 1-3.5 h;
(5) And (3) placing the mold after microwave curing into a curing box for steam curing, wherein the curing temperature is 40-80 ℃, and demolding after curing for 20.5-23 h to obtain the low-carbon cementing material with high early strength.
5. The processing method of the low-carbon cementing material with high early strength as claimed in claim 4, wherein the mold is a Polyetheretherketone (PEEK) triple mold.
6. The processing method of the early-stage high-strength low-carbon cementing material as claimed in claim 4, wherein in the step (4), water is added into the mold during the microwave heating process to keep the relative humidity in the mold to be more than 95%.
7. The processing method of the early-stage high-strength low-carbon cementing material according to the claim 4, characterized in that the microwave curing temperature in the step (4) is 100 ℃, and the curing time is 2.5h.
8. The method for processing the low-carbon cementing material with high early strength as claimed in claim 4, wherein the steam curing temperature in step (5) is 80 ℃ and the curing time is 21.5h.
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| CN116375430A (en) * | 2023-04-27 | 2023-07-04 | 中南大学 | Lead smelting water quenching slag-based cementing material, and preparation method and application thereof |
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