CN113563107A - Cement-based material and preparation method thereof - Google Patents
Cement-based material and preparation method thereof Download PDFInfo
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- CN113563107A CN113563107A CN202110828249.1A CN202110828249A CN113563107A CN 113563107 A CN113563107 A CN 113563107A CN 202110828249 A CN202110828249 A CN 202110828249A CN 113563107 A CN113563107 A CN 113563107A
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- 239000004568 cement Substances 0.000 title claims abstract description 122
- 239000000463 material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 15
- 230000033558 biomineral tissue development Effects 0.000 claims description 15
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 14
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 10
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 6
- 230000001089 mineralizing effect Effects 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 abstract description 39
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011575 calcium Substances 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 3
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 55
- 229910002092 carbon dioxide Inorganic materials 0.000 description 31
- 239000004567 concrete Substances 0.000 description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000012423 maintenance Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- 235000012241 calcium silicate Nutrition 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 2
- 235000019976 tricalcium silicate Nutrition 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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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
- C04B40/0263—Hardening promoted by a rise in temperature
-
- 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
- C04B24/121—Amines, polyamines
-
- 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
-
- 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
- C04B24/128—Heterocyclic nitrogen compounds
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention relates to a cement-based material and a preparation method thereof, wherein the preparation method of the cement-based material comprises the following steps: mixing the raw materials of the cement-based material, adding the amine additive in the mixing process of the raw materials, adding water, stirring and forming, and carrying out high-temperature pretreatment and CO2Mineralizing and maintaining; wherein the addition amount of the amine admixture is 0.01-2 per mill of the mass of cement in the raw materials. According to the invention, the amine admixture is added in the raw material mixing process, so that the internal micropore structure of the cement-based material can be adjusted, and the CO is improved2Solubility and dissolution rate of calcium and magnesium ions, and effectively improves CO2The carbonization reaction depth is increased, and the CO content in the cement-based material is improved2The carbonization rate has better energy-saving and carbon-reducing effects. By the method of the inventionThe obtained cement-based material has a carbonization rate of 28-35%.
Description
Technical Field
The invention relates to the technical field of concrete curing, in particular to a cement-based material and a preparation method thereof.
Background
CO2The mineralization curing technology utilizes early-formed concrete material and CO2The carbonation reaction and the product deposition process between the components realize the improvement of the mechanical strength and other characteristics of the product, and mainly pay attention to the gelling component and CO in the concrete after the pretreatment/early hydration forming2In between mineralisation and curing (i.e. accelerated carbonation) during which hydration of the cementitious material is no longer the primary reaction for strength formation.
Calcium silicate and CO2Fast reaction and higher strength in a short period, theoretically, portland cement and CO2CO after complete reaction2The consumption can reach about 50 percent of the cement quality, but the cement and CO are maintained under the conventional maintenance mode2The reaction degree is not more than 15%, the hardening period can be quickly shortened through mineralization curing, and the carbonization curing reaction degree is improved to about 20%, but still far lower than the theoretical carbon fixation rate.
Surrounding CO2In the technology of mineralizing and curing cement-based materials, a great deal of research work has been carried out by domestic and foreign research institutions, but most of the research focuses on improving the mechanical properties of the cement-based materials by optimizing a curing system, adjusting a water-cement ratio and the like. At present, the adopted technology comprises the steps of mixing supercritical carbon dioxide with cement and sandstone together to realize carbon dioxide mineralization; or curing the concrete with low water-cement ratio under high pressure by using carbon dioxide. However, these methods have problems of difficulty in operation, high cost, and the like.
Disclosure of Invention
The invention mainly aims to provide a cement-based material and a preparation method thereof, and aims to solve the technical problem of improving CO (carbon monoxide) by adding amine substances into the cement-based material to adjust the internal pore structure of the cement-based material2Diffusion and calcium and magnesium ionsThe dissolution conditions of (3) promote the improvement of the carbonization depth.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The preparation method of the cement-based material provided by the invention comprises the following steps:
mixing the raw materials of the cement-based material, adding the amine additive in the mixing process of the raw materials, adding water, stirring and forming, and carrying out high-temperature pretreatment and CO2Mineralizing and maintaining; wherein the addition amount of the amine admixture is 0.01-2 per mill of the mass of cement in the raw materials.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the method for preparing cement-based materials is described above, wherein the amine additive is at least one selected from monoethanolamine, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, piperazine, N-methyldiethanolamine, N-diethylethanolamine, and triethylenetetramine.
Preferably, in the preparation method of the cement-based material, the amine admixture comprises the following components in percentage by mass: 10-30% of monoethanolamine and 70-90% of 2-amino-2 methyl-1-propanol.
Preferably, in the preparation method of the cement-based material, the amine admixture comprises the following components in percentage by mass: 5-20% of monoethanolamine and 80-95% of N-methyldiethanolamine.
Preferably, in the preparation method of the cement-based material, the amine admixture comprises the following components in percentage by mass: 25-40% of N-methyldiethanolamine, 25-40% of 2-amino-2-methyl-1-propanol and 20-50% of N, N-diethylethanolamine.
Preferably, in the preparation method of the cement-based material, the temperature of the high-temperature pretreatment is 100-200 ℃, the time is 10-60 min, and the atmosphere is normal pressure air.
Preferably, the method for preparing a cement-based material, wherein said CO is2The temperature of mineralization curing is 40-90 ℃, and the pressure is 0.1-up to2MPa，CO2The partial pressure is 20 to 100 percent, and the time is 0.5 to 12 hours.
Preferably, the method for preparing a cement-based material, wherein said CO is2The time for mineralizing and curing is 2-8 h.
Preferably, in the preparation method of the cement-based material, the raw materials of the cement-based material comprise, by mass: 10-100% of cement;
the addition amount of the amine admixture is 0.5-1.5 per mill of the mass of the cement.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The cement-based material provided by the invention has the carbonization rate of 28-35%.
By the technical scheme, the cement-based material and the preparation method thereof provided by the invention at least have the following advantages:
1. the invention provides a method for passing CO2Method for obtaining cement-based materials by mineralizing and curing, CO2The mineralization maintenance can mineralize and fix CO2Meanwhile, the rapid curing and forming of concrete are promoted, the polymerization of carbonated products forms the material strength, and the CO can be effectively improved by adding the amine additive in the mixing process of the raw materials of the cement-based material2The carbonization reaction depth is increased, and the CO content in the cement-based material is improved2The solidification rate, and then improve the carbonization rate of the cement-based material, and simultaneously can also improve the compressive strength of the cement-based material.
2. Compared with the existing autoclaved curing technology, the method of the invention passes through CO under the action of amine additives2The mineralization maintenance can effectively improve CO2The carbonization reaction depth is improved, the carbonization rate of the cement-based material is improved, the cement-based material can meet the strength requirement in a short time, the operation cost is reduced, and CO can be solidified2The carbon emission is obviously reduced, the energy-saving and carbon-reducing effects are better, and the market prospect and the economic value are wide.
3. According to the technical scheme, the amine admixture is introduced in the mixing process of the raw materials of the cement-based material, and the amine admixture is mixed with water in the mixing processThe amine additive can be further diffused in the gap structure of the cement-based material through high-temperature air pretreatment, so that the pore channel is more unobstructed and open, and CO is convenient to disperse on the surfaces of raw material particles of the cement-based material2The transmission in the pores promotes the dispersion of the additive and the dissolution of calcium and magnesium ions, and improves the CO in the mineralization and maintenance stage2The solubility of the compound promotes the reaction of carbon dioxide and mineral phases such as C3S, C2S and the like in the cement concrete; by CO2The mineralizing maintenance is carried out, and the amine additive can effectively capture and diffuse CO in the pores of the cement-based material2The method improves the mineralization maintenance depth of the cement-based material, is convenient for the reaction of the cement-based material with dicalcium silicate, tricalcium silicate, calcium hydroxide and the like in the cement-based material to form calcium carbonate and silica gel, and quickly improves the strength of the cement-based material.
4. The invention is based on the research of cement-based material admixture and chemical absorption carbon trapping technology, and can adjust the internal micropore structure of the cement-based material and improve CO by adding amine substances such as triethanolamine, triisopropanolamine and the like2Solubility and dissolution rate of calcium and magnesium ions, and effectively improves CO2The carbonization reaction depth is increased, and the CO content in the cement-based material is improved2And (4) curing rate.
5. The cement-based material obtained by the method has the carbonization rate of 28-35 percent and higher compressive strength.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the concrete embodiments, structures, characteristics and effects of the cement-based material and the preparation method thereof according to the present invention in combination with the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
One embodiment of the present invention provides a method for preparing a cement-based material, comprising: mixing the raw materials of the cement-based material, adding the amine additive in the mixing process of the raw materials, adding water, stirring and forming, and carrying out high-temperature pretreatment and CO2Mineralizing and maintaining; wherein the addition amount of the amine admixture is 0.01-2 per mill of the mass of cement in the raw materials.
When the addition amount of the amine additive is less than 0.01 per mill, the expected effect cannot be achieved due to too small addition amount of the amine, and the strength of the cement-based material is easily shrunk due to too large addition amount of the amine additive, so that the service performance and durability of products are affected, and the production cost is increased.
According to the embodiment of the invention, by adding the amine additive, preferably the alcohol amine, the carbon dioxide mineralization curing depth can be improved, and meanwhile, the strength of the cement-based material can be improved.
In the present embodiment, the cement-based material refers to an engineering material having cement as a binding material. Concrete, mortar are the most common cement-based materials. And cement-based grouting materials, cement-based paints, and the like.
The cement-based material of the present embodiment may be a cement product using cement as a raw material, or a product produced using cement as a main raw material, for example, a composite material mainly using portland cement as a matrix, to which sand, crushed stone, fly ash, mineral powder, and the like are added, and which is formed by a composite process.
In some embodiments, the amine additive is selected from at least one of monoethanolamine, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, piperazine, N-methyldiethanolamine, N-diethylethanolamine, and triethylenetetramine.
In some preferred embodiments, the amine admixture consists of the following components in percentage by mass: 10-30% of monoethanolamine and 70-90% of 2-amino-2 methyl-1-propanol.
In other preferred embodiments, the amine admixture consists of the following components in percentage by mass: 5-20% of monoethanolamine and 80-95% of N-methyldiethanolamine.
In some preferred embodiments, the amine admixture consists of the following components in percentage by mass: 25-40% of N-methyldiethanolamine, 25-40% of 2-amino-2-methyl-1-propanol and 20-50% of N, N-diethylethanolamine.
In some embodiments, the high-temperature pretreatment is performed at 100-200 ℃ for 10-60 min in a normal-pressure air atmosphere.
In some embodiments, the CO is2The temperature of mineralization curing is 40-90 ℃, the pressure is 0.1-2 MPa, and CO is2The partial pressure is 20 to 100 percent, and the time is 0.5 to 12 hours.
Further, said CO2The time for mineralizing and curing is 2-8 h.
CO2The mineralization maintenance can mineralize and fix CO2Meanwhile, the rapid curing and forming of concrete are promoted, and the polymerization of carbonated products forms the material strength, CO2The mineralization maintenance generally occurs at the gas, liquid and solid three-phase cross section, and the main reaction steps include: CO 22The solution enters interface pore solution for dissolution, alkali metal ions in solid minerals are separated out and enter the pore solution, and the reaction and precipitation of carbonate ions and alkali metal ions in the pore solution are carried out.
The amine admixture and water are dispersed on the surfaces of raw material particles of the cement-based material together in the mixing process. In the high-temperature pretreatment process, the amine additive can be further diffused in the void structure of the cement-based material, so that the pore channel is more unobstructed and open, and CO is convenient to remove2The transmission in the pores improves the mineralization curing depth of the cement-based material. In the process of mineralization and maintenance, the amine additive can effectively capture CO diffused into pores of the cement-based material2The calcium silicate-silica gel-based cement-based material can react with dicalcium silicate, tricalcium silicate, calcium hydroxide and the like in the cement-based material to form calcium carbonate and silica gel, so that the strength of the cement-based material is rapidly improved.
Compared with the existing autoclaved curing technology, the method of the invention can enable the cement-based material to reach the strength requirement in a short time, and reduce the operation costAt the same time, CO can be solidified2The carbon emission is obviously reduced, and the method has wide market prospect and economic value.
Another embodiment of the present invention provides a cement-based material having a carbonation rate of 28 to 35%.
The cement-based material of the embodiment is prepared by the preparation method of the cement-based material.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
In the following examples of the present invention, all reagents used are commercially available unless otherwise specified, and the methods involved are conventional unless otherwise specified.
Example 1
(1) Taking 100kg of reference cement, adding 10g (0.1 per mill by mass) of triethanolamine, and mixing according to the water cement ratio of 0.4 to prepare a cement paste test block; taking the same batch of cement and making blank test blocks according to the same water cement ratio;
(2) placing the formed clean pulp test block in an air atmosphere, and pretreating at 120 ℃ for 30 min;
(3) placing the test block obtained in the step (2) in CO2Under mineralized curing atmosphere, the curing pressure is 0.2MPa, and CO is2Maintaining for 4 hours at the temperature of 40-50 ℃ with the partial pressure of 80 percent.
The carbonization rate and the compressive strength of the cement paste test block and the blank test block in example 1 are shown in table 1.
TABLE 1 carbonization rate and compressive strength
| Carbonization rate/%) | Compressive strength/MPa | |
| Example 1 | 30 | 47 |
| Blank test block | 24 | 39 |
Example 2
(1) Taking 100kg of reference cement, adding 30g (0.3 per mill of mass) of triisopropanolamine, and mixing according to the water cement ratio of 0.35 to prepare a cement paste test block; taking the same batch of cement and making blank test blocks according to the same water cement ratio;
(2) placing the formed clean pulp test block in an air atmosphere, and pretreating at 130 ℃ for 20 min;
(3) placing the test block obtained in the step (2) in CO2Under mineralized curing atmosphere, the curing pressure is 0.3MPa, and CO is2Maintaining for 2 hours at 50-60 ℃ with the partial pressure of 90 percent.
The results of the tests show that the carbonization rate and the compressive strength of the cement paste test block and the blank test block in example 2 are shown in Table 2.
TABLE 2 carbonization rate and compressive strength
| Carbonization rate/%) | Compressive strength/MPa | |
| Example 2 | 28.5 | 45.8 |
| Blank test block | 23.6 | 42.9 |
Example 3
(1) 100kg of P.O.42.5 cement, 325kg of sand, 450kg of broken stone, 23.5kg of fly ash and 33kg of mineral powder are taken, 100g of ethanolamine, 30g of 2-amino-2-methyl-1-propanol and 50g of piperazine are added, and are mixed according to the water-cement ratio of 0.42 to prepare a concrete test block; taking the raw materials of the same batch in a mixing ratio, and making a blank test block without adding an additive;
(2) placing the formed concrete test block in an air atmosphere, and pretreating at 100 ℃ for 40 min;
(3) placing the test block obtained in the step (2) in CO2Under mineralized curing atmosphere, the curing pressure is 0.1MPa, and CO is2Maintaining at a partial pressure of 30% and a temperature of about 90 ℃ for 6 h.
The concrete test block and the blank test block of example 3 have the carbonization rate and the compressive strength shown in Table 3.
TABLE 3 carbonization rate and compressive strength
| Carbonization rate/%) | Compressive strength/MPa | |
| Example 4 | 28.6 | 18.9 |
| Blank test block | 24.4 | 12.5 |
Example 4
(1) Taking 100kg of P.O.42.5 cement, 200kg of sand and 350kg of broken stone, adding 10g of triisopropanolamine, 25g of N-methyldiethanolamine and 25g of N, N-diethylethanolamine, and mixing according to the water-cement ratio of 0.35 to prepare a concrete test block; taking the raw materials of the same batch in a mixing ratio, and making a blank test block without adding an additive;
(2) placing the formed concrete test block in an air atmosphere, and pretreating at 200 ℃ for 30 min;
(3) placing the test block obtained in the step (2) in CO2Under mineralized curing atmosphere, the curing pressure is 2MPa, and CO is2Maintaining at a partial pressure of 50% for 2h at a temperature of about 60 ℃.
The concrete test block and the blank test block of example 4 have the carbonization rate and the compressive strength shown in Table 4.
TABLE 4 carbonization rate and compressive strength
| Carbonization rate/%) | Compressive strength/MPa | |
| Example 4 | 30.2 | 19.5 |
| Blank test block | 26 | 15.6 |
Example 5
(1) Taking 100kg of P.O.42.5 cement, 300kg of sand and 250kg of broken stone, adding 10g of triethanolamine and 50g of triethylene tetramine, and mixing according to the water cement ratio of 0.25 to prepare a concrete test block; taking the raw materials of the same batch in a mixing ratio, and making a blank test block without adding an additive;
(2) placing the formed concrete test block in an air atmosphere at 150 ℃, and pretreating for 60 min;
(3) placing the test block obtained in the step (2) in CO2Under mineralized curing atmosphere, the curing pressure is 0.5MPa, and CO is2Maintaining at a partial pressure of 70% at 60 deg.C for 2 h.
The concrete test block and the blank test block of example 5 have the carbonization rate and the compressive strength shown in Table 5.
TABLE 5 carbonization rate and compressive strength
| Carbonization rate/%) | Compressive strength/MPa | |
| Example 5 | 29.5 | 18.5 |
| Blank test block | 25.3 | 15.6 |
Examples 6 to 10
(1) Taking 100kg of reference cement, respectively adding the amine additives in the table 6 into the reference cement, and mixing according to the water cement ratio of 0.4 to prepare a cement paste test block; taking the raw materials of the same batch in a mixing ratio, and making a blank test block without adding an additive;
(2) placing the formed clean pulp test block in an air atmosphere, and pretreating at 120 ℃ for 30 min;
(3) placing the test block obtained in the step (2) in CO2Under mineralized curing atmosphere, the curing pressure is 0.2MPa, and CO is2Maintaining for 4 hours at the temperature of 40-50 ℃ with the partial pressure of 80 percent.
The results of the tests show that the carbonization rates and compressive strengths of the cement paste test pieces and the blank test pieces of examples 6-10 are shown in Table 6.
TABLE 6 carbonization rate and compressive strength
Examples 11 to 23
(1) Taking 100kg of reference cement, respectively adding the amine additives in the table 7 into the reference cement, and mixing according to the water cement ratio of 0.4 to prepare a cement paste test block;
(2) placing the formed clean pulp test block in an air atmosphere, and pretreating at 120 ℃ for 30 min;
(3) placing the test block obtained in the step (2) in CO2Under mineralized curing atmosphere, the curing pressure is 0.2MPa, and CO is2Maintaining for 4 hours at the temperature of 40-50 ℃ with the partial pressure of 80 percent.
The measured carbonization rates and compressive strengths of the cement paste test pieces of examples 11-23 are shown in Table 7.
TABLE 7 carbonization rate and compressive strength
As can be seen from tables 1-6, the carbonation rate and the compressive strength of the test block are greatly improved by adding the amine admixture into the cement-based material.
As can be seen from Table 7, the combination of two or more amines can produce a synergistic effect and increase the product towards CO2The adsorption performance of the cement-based material is improved, the carbonization rate of the cement-based material is improved, and the compressive strength is also improved to a certain degree. Under the same amine doping amount, the carbonization rate and the compressive strength ratio of the 20 percent of monoethanolamine and 80 percent of N-methyldiethanolamine used in example 13 are obviously better than those of the monoethanolamine or the N-methyldiethanolamine added in example 11 or 12, indicating that the doping effect of the monoethanolamine and the N-methyldiethanolamine is better than that of the monoethanolamine and the N-methyldiethanolamine added in example 11 or 12, indicating that the two substances have mutual promotion and mutual synergistic effect. The carbonization rate and the compressive strength of example 16 are significantly better than those of example 14 or example 15, the carbonization rate and the compressive strength of example 20 are significantly better than those of example 17, example 18 or example 19, and the carbonization rate and the compressive strength of example 23 are significantly better than those of example 21 or example 22.
The carbonization rate and the compressive strength in the invention are detected according to the following methods:
the detection method of the carbonization rate comprises the following steps: weighing the pretreated test block, and recording the weight as m0Placing the mineralized and cured test block in a sealed container for vacuumizing treatment, wherein the vacuum degree is less than or equal to-0.03 MPa, then placing the test block in air, and weighing the test block to record the weight as m; CO 22Absorption M-M0(ii) a Calculating CO from Cement Components2Theoretical absorption Wmax＝0.785(CaO-0.7SO3)+1.09MgO+1.42Na2O+0.93K2O; carbonization rate M/(W)maxMass of cement in x test block).
The compressive strength of the slurry-removed test block is detected according to the standard GB/T17671-2020 Cement mortar Strength inspection method (ISO method);
the compressive strength of the concrete test block is detected according to GB/T50080-2016 Standard test method for the Performance of common concrete mixtures.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method of preparing a cementitious material, comprising:
mixing the raw materials of the cement-based material, adding the amine additive in the mixing process of the raw materials, adding water, stirring and forming, and carrying out high-temperature pretreatment and CO2Mineralizing and maintaining; wherein the addition amount of the amine admixture is 0.01-2 per mill of the mass of cement in the raw materials.
2. The method of producing a cementitious material as claimed in claim 1,
the amine additive is at least one selected from monoethanolamine, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, piperazine, N-methyldiethanolamine, N-diethylethanolamine and triethylenetetramine.
3. A method of producing a cementitious material as claimed in claim 2,
the amine admixture comprises the following components in percentage by mass: 10-30% of monoethanolamine and 70-90% of 2-amino-2 methyl-1-propanol.
4. A method of producing a cementitious material as claimed in claim 2,
the amine admixture comprises the following components in percentage by mass: 5-20% of monoethanolamine and 80-95% of N-methyldiethanolamine.
5. A method of producing a cementitious material as claimed in claim 2,
the amine admixture comprises the following components in percentage by mass: 25-40% of N-methyldiethanolamine, 25-40% of 2-amino-2-methyl-1-propanol and 20-50% of N, N-diethylethanolamine.
6. The method of producing a cementitious material as claimed in claim 1,
the high-temperature pretreatment is carried out at the temperature of 100-200 ℃ for 10-60 min in the atmosphere of normal-pressure air.
7. The method of producing a cementitious material as claimed in claim 1,
said CO2The temperature of mineralization curing is 40-90 ℃, the pressure is 0.1-2 MPa, and CO is2The partial pressure is 20 to 100 percent, and the time is 0.5 to 12 hours.
8. A method of producing a cementitious material as claimed in claim 7,
said CO2The time for mineralizing and curing is 2-8 h.
9. The method of producing a cementitious material as claimed in claim 1,
the cement-based material comprises the following raw materials in percentage by mass: 10-100% of cement;
the addition amount of the amine admixture is 0.5-1.5 per mill of the mass of the cement.
10. The cement-based material is characterized in that the carbonation rate of the cement-based material is 28-35%.
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| CN114538850A (en) * | 2022-03-09 | 2022-05-27 | 南京工业大学 | Solid waste base lightweight aggregate based on biochar internal carbonization and preparation method thereof |
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| CN114988749A (en) * | 2022-07-18 | 2022-09-02 | 北京工业大学 | Resource utilization method for capturing carbon dioxide |
| 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 |
| CN115557755A (en) * | 2022-11-03 | 2023-01-03 | 华新水泥股份有限公司 | Low-calcium carbon-fixing regenerated pervious concrete and production method thereof |
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