CN116161886A - Low-carbon gelling material based on low-grade high-magnesium limestone and preparation method thereof - Google Patents
Low-carbon gelling material based on low-grade high-magnesium limestone and preparation method thereof Download PDFInfo
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- CN116161886A CN116161886A CN202310157838.0A CN202310157838A CN116161886A CN 116161886 A CN116161886 A CN 116161886A CN 202310157838 A CN202310157838 A CN 202310157838A CN 116161886 A CN116161886 A CN 116161886A
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- 235000019738 Limestone Nutrition 0.000 title claims abstract description 94
- 239000006028 limestone Substances 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 239000011777 magnesium Substances 0.000 title claims abstract description 41
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 49
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 40
- 235000003704 aspartic acid Nutrition 0.000 claims abstract description 40
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims abstract description 40
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004568 cement Substances 0.000 claims abstract description 35
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 27
- 239000010440 gypsum Substances 0.000 claims abstract description 25
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 25
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002210 silicon-based material Substances 0.000 claims abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims description 37
- 238000000354 decomposition reaction Methods 0.000 claims description 20
- 239000004927 clay Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 239000010881 fly ash Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000395 magnesium oxide Substances 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 11
- 239000001095 magnesium carbonate Substances 0.000 description 11
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 7
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Classifications
-
- 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
- C04B9/00—Magnesium cements or similar cements
- C04B9/11—Mixtures thereof with other inorganic cementitious materials
- C04B9/12—Mixtures thereof with other inorganic cementitious materials with hydraulic cements, e.g. 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
- C04B9/00—Magnesium cements or similar cements
- C04B9/20—Manufacture, e.g. preparing the batches
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a low-carbon cementing material based on low-grade high-magnesium limestone and a preparation method thereof, wherein the cementing material comprises the following preparation raw materials in percentage by mass: 15-45% of limestone, 20-60% of aluminum-silicon material, 5-10% of gypsum, 0.5-3% of aspartic acid, 0.5-1.8% of 2-amino terephthalic acid and nano Al 2 O 3 1.5-14.2% and 13-40% of cement clinker; the sum of the mass fractions of the raw materials is 100 percent; wherein the limestone is low-grade high-magnesium limestone with the mass content of magnesium being more than 4 percent. The low-carbon gelling material based on the low-grade high-magnesium limestone and the preparation method thereof provided by the invention can promote the resource utilization of the low-grade high-magnesium limestone, so that the original harmful MgCO is realized 3 Becomes an essential component in the novel cement, can solve the core difficult problem of large-scale utilization of the magnesium-containing limestone, and has good popularization and application prospect.
Description
Technical Field
The invention relates to the field of cementing materials, in particular to a low-carbon cementing material based on low-grade high-magnesium-content limestone and a preparation method thereof.
Background
Limestone is widely used in the preparation of cement building materials, such as calcining lime or cement as a raw material, or as a mixture or admixture. The use of limestone as a mix or admixture is an important way of use, both as an inert filler to regulate the workability of cement concrete and as an active component to prepare novel binders, such as limestone-aluminosiliceous auxiliary binders, which utilize the carbonate in limestone to react with the active aluminium in the active aluminosiliceous mineral to produce a cementitious component that achieves higher mechanics and durability, but the reaction process is greatly affected by the solubility of the carbonate in the limestone.
In addition, the taste of limestone is reduced to become a huge pain point in the industry, wherein the MgO content exceeding 4% is a common characteristic of low-grade limestone, and the limestone is used for preparing silicate cement, and the cement is easy to crack and generate instability due to the slow reaction after hardening due to the residual free magnesium oxide.
Therefore, the current use of low grade limestone with high magnesium content in cementitious materials encounters difficulties and improvements in the prior art are needed to provide a reliable solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-carbon gelling material based on low-grade high-magnesium limestone and a preparation method thereof. Aiming at the application difficulty of low-grade magnesium-containing limestone, the limestone is firstly subjected to controllable calcination to obtain a product with a certain decomposition rate and activity, then is compounded with aluminum-silicon auxiliary cementing materials (such as mineral powder, calcined clay and fly ash) and other auxiliary materials (gypsum, aspartic acid, 2-amino terephthalic acid, nanometer and cement clinker) and the like, finally is subjected to carbonization treatment, and high-reactivity carbonate (magnesium carbonate) is obtained through the regulation and control of the crystal form of the carbonized product, so that the hydration of the aluminum phase is promoted to participate in the preparation of the high-performance low-carbon cementing material.
In order to achieve the above purpose, the invention adopts the following technical scheme: a low-carbon gelling material based on low-grade high-magnesium limestone comprises the following preparation raw materials in percentage by mass:
15% -45% of limestone;
20-60% of aluminum-silicon material;
5-10% of gypsum;
aspartic acid 0.5% -3%;
0.5-1.8% of 2-amino terephthalic acid;
nano Al 2 O 3 1.5-14.2％；
13-40% of cement clinker;
the sum of the mass fractions of the raw materials is 100 percent;
wherein the limestone is low-grade high-magnesium limestone with the mass content of magnesium being more than 4 percent.
Preferably, the limestone is calcined and decomposed before being used, and the decomposition rate of the limestone is controlled to be 6.7-92.5%.
Preferably, the aluminum-silicon material is one or more of calcined clay, mineral powder, high collar clay, fly ash, calcined coal gangue and calcined tailing slurry.
Preferably, the preparation raw materials of the low-carbon gelling material based on the low-grade high-magnesium limestone comprise the following components in percentage by mass:
40% of limestone;
28% of an aluminum-silicon material;
gypsum 9%;
aspartic acid 2%;
1.2% of 2-amino terephthalic acid;
nano Al 2 O 3 2％；
The balance of cement clinker;
the sum of the mass fractions of the raw materials is 100 percent.
Preferably, the preparation raw materials of the low-carbon gelling material based on the low-grade high-magnesium limestone comprise the following components in percentage by mass:
40% of limestone;
28% of an aluminum-silicon material;
gypsum 9%;
aspartic acid 1.5%;
2-amino terephthalic acid 0.8%;
nano Al 2 O 3 2％；
The balance of cement clinker;
the sum of the mass fractions of the raw materials is 100 percent.
Preferably, the limestone is calcined and decomposed before being used, and the decomposition rate of the limestone is controlled to be 91.3%.
Preferably, the alumina-silica material is calcined clay.
The invention also provides a preparation method of the low-carbon gelling material based on the low-grade high-magnesium limestone, which comprises the following steps:
s1, weighing the raw materials according to the mass ratio;
s2, calcining the limestone at 710-820 ℃ and controlling the decomposition rate of the limestone to be 6.7-92.5%;
s3, mixing the calcined product obtained in the step S2 with other raw materials weighed in the step S1: aluminum-silicon material, gypsum, aspartic acid, 2-amino terephthalic acid and nano Al 2 O 3 Mixing the cement clinker uniformly to obtain a primary product;
and S4, carbonizing the initial product obtained in the step S3 to obtain the high-performance low-carbon gel material.
Preferably, the carbonization conditions in the step S4 are: carbonization temperature range of 20-80 ℃, CO 2 The mass concentration range is 5-20%, the carbonization pressure is 1-10atm, the carbonization time is 5-8 hours, and the humidity is 50-90%.
Preferably, the preparation method of the low-carbon gelling material based on the low-grade high-magnesium limestone comprises the following steps of:
s1, weighing the raw materials according to the mass ratio;
s2, calcining the limestone at 750 ℃ and controlling the decomposition rate of the limestone to be 91.3%;
s3, mixing the calcined product obtained in the step S2 with other raw materials weighed in the step S1: aluminum-silicon material, gypsum, aspartic acid, 2-amino terephthalic acid and nano Al 2 O 3 Mixing the cement clinker uniformly to obtain a primary product;
s4, carbonizing the initial product obtained in the step S3 to obtain the high-performance low-carbon gel material;
wherein, carbonization conditions are: carbonization temperature range 50 ℃, CO 2 The mass concentration range is 10%, the carbonization pressure is 5atm, the carbonization time is 6.5 hours, and the humidity is 70%.
The beneficial effects of the invention are as follows:
the low-carbon gelling material based on the low-grade high-magnesium limestone and the preparation method thereof provided by the invention can promote the resource utilization of the low-grade high-magnesium limestone, so that the original harmful MgCO is realized 3 Becomes an essential component in the novel cement, can solve the core problem of large-scale utilization of the magnesium-containing limestone, and has good popularization and application prospect;
in the invention, the magnesium carbonate crystal form is regulated and controlled by aspartic acid and 2-amino terephthalic acid, so that the MgCO with high solubility can be improved 3 The content of the aluminum-containing gel material further promotes the capability of the gel material in opposite to aluminum, and can effectively improve the strength of the gel material;
in the invention, the CaO and MgO with high hydration and carbonization activities obtained by the low-temperature calcination of the raw material limestone can provide high-activity raw materials for the performance development of the cementing material, wherein part of the raw material is not decomposed dolomite CaMg (CO 3 ) 2 Can be used as filler or provide raw materials for later reaction, and has low decomposition temperature and energy consumption saving.
Drawings
FIG. 1 is a scanning electron microscope photograph of a magnesium carbonate crystal form obtained by carbonizing MgO without adding aspartic acid and 2-amino terephthalic acid;
FIG. 2 is a scanning electron micrograph of a magnesium carbonate crystal form obtained by carbonizing MgO with only aspartic acid added;
FIG. 3 is a scanning electron micrograph of a magnesium carbonate crystal form obtained by carbonizing MgO with the addition of aspartic acid and 2-aminoterephthalic acid.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a low-carbon gelling material based on low-grade high-magnesium limestone, which comprises the following preparation raw materials in percentage by mass:
15 to 45 percent of limestone
20-60% of aluminum-silicon material;
5-10% of gypsum;
aspartic acid 0.5% -3%;
0.5-1.8% of 2-amino terephthalic acid;
nano Al 2 O 3 1.5-14.2％
13-40% of cement clinker;
the sum of the mass fractions of the raw materials is 100 percent;
wherein the limestone is low-grade high-magnesium limestone with the mass content of magnesium being more than 4 percent.
Wherein, the limestone is calcined and decomposed at 710-820 ℃ and then used, the decomposition rate of the limestone is controlled to be 6.7-92.5%, and the calcined product mainly contains CaO, mgO and CaMg (CO) 3 ) 2 . In the present invention,the CaO and MgO obtained by low-temperature calcination have high hydration and carbonization activities, can provide high-activity raw materials for the performance development of the cementing material, have low decomposition temperature and can save energy consumption; wherein part of the undissolved dolomite is CaMg (CO 3 ) 2 Can be used as filler or provide raw materials for later reaction, and can effectively expand the application range of the raw materials, namely, the decomposition rate is controlled according to the later reaction activity of the raw materials: the decomposition rate can be controlled to be reduced for high reactive aluminosilicate minerals and increased for low reactive aluminosilicate minerals.
Wherein the aluminum-silicon material is one or more of calcined clay, mineral powder, high collar clay, fly ash, calcined coal gangue and calcined tailing slurry.
The invention also provides a preparation method of the low-carbon gelling material based on the low-grade high-magnesium limestone, which comprises the following steps:
s1, weighing the raw materials according to the mass ratio;
s2, calcining the limestone at 710-820 ℃ and controlling the decomposition rate of the limestone to be 6.7-92.5%;
s3, mixing the calcined product obtained in the step S2 with other raw materials weighed in the step S1: aluminum-silicon material, gypsum, aspartic acid, 2-amino terephthalic acid and nano Al 2 O 3 Mixing the cement clinker uniformly to obtain a primary product;
s4, carbonizing the initial product obtained in the step S3 to obtain the high-performance low-carbon gel material; the carbonization conditions are as follows: carbonization temperature range of 20-80 ℃, CO 2 The mass concentration range is 5-20%, the carbonization pressure is 1-10atm, the carbonization time is 5-8 hours, and the humidity is 50-90%.
In the invention, the reaction principle of the cementing material is as follows: hydration and carbonization of CaO and MgO to form cementing capacity, and subsequent carbonation to form CaCO 3 And MgCO 3 Partially undissolved dolomite CaMg (CO 3 ) 2 These differently soluble carbonates can provide the system with performance developing feedstock components at different times (early and late middle stages) that can react with aluminosilicates to form gelled products.
In the present inventionThe added aspartic acid can control the formed MgCO by adsorbing on the MgO surface 3 The species and solubility can improve the solubility of MgCO 3 Trihydromagnesite (MgCO) 3 ·3H 2 O), thereby improving the reactivity; the aspartic acid regulates and controls the crystal form of the magnesium carbonate, so as to regulate and control the solubility of the magnesium carbonate, and the regulation and control mechanism is as follows: the carboxyl of aspartic acid and Mg ions are complexed through common electrons, so that the concentration of Mg ions in the system is improved, the reaction of Mg and carbon dioxide is promoted, and soluble MgCO is generated 3 The method comprises the steps of carrying out a first treatment on the surface of the Aspartic acid can also be combined with the soluble MgCO formed 3 ·3H 2 O is complexed to further inhibit the conversion of MgCO into MgCO with low solubility 3 The content of the large-solubility magnesium carbonate is improved, the capability of opposing to aluminum is further promoted, and the strength is improved;
wherein, the added 2-amino terephthalic acid can improve the solubility of carbonate by complexing metal Mg ions, thereby improving the reaction capability; and 2-amino terephthalic acid and aspartic acid are used for improving high-solubility MgCO 3 The content can play a role in synergistic enhancement: 2-amino terephthalic acid chelates with magnesium oxide and serves as a nucleation site to allow the surface to dissolve out more Mg ions and OH ions. The carboxyl of aspartic acid and a large amount of Mg ions generated under the action of 2-amino terephthalic acid are subjected to common electron complexing, so that the concentration of the Mg ions in the system is greatly improved; meanwhile, due to the addition of the 2-amino terephthalic acid, the concentration of OH ions in the system is increased, the pH value is increased, the dissolution of carbon dioxide is promoted, and the carbonization degree of magnesium oxide is further improved.
In the invention, by adding nano Al 2 O 3 Can improve the content of active aluminum in the system, improve early hydration reaction and promote early strength improvement.
The foregoing is a general inventive concept and the following detailed examples and comparative examples are provided on the basis thereof to further illustrate the invention.
In the following examples and comparative examples, the mass fraction of magnesium in limestone was 4.6% and originated from a certain cement mine; nanometer gamma-Al 2 O 3 In particular gamma-Al 2 O 3 The particle size is 50nm, and the product is a commercial product;the remaining unidentified manufacturers are conventional products available commercially.
Example 1
A low-carbon gelling material based on low-grade high-magnesium limestone comprises the following preparation raw materials in percentage by mass: 40% of limestone, 28% of calcined clay, 9% of gypsum, 2% of aspartic acid, 1.2% of 2-amino terephthalic acid and nano Al 2 O 3 2% and 17.8% of cement clinker.
The preparation method comprises the following steps:
s1, weighing the raw materials according to the mass ratio;
s2, calcining the limestone at 750 ℃ and controlling the decomposition rate of the limestone to be 91.3%;
s3, mixing the calcined product obtained in the step S2 with other raw materials weighed in the step S1: aluminum-silicon material, gypsum, aspartic acid, 2-amino terephthalic acid and nano Al 2 O 3 Mixing the cement clinker uniformly to obtain a primary product;
s4, carbonizing the initial product obtained in the step S3 to obtain the high-performance low-carbon gel material;
wherein, carbonization conditions are: carbonization temperature range 50 ℃, CO 2 The mass concentration range is 10%, the carbonization pressure is 5atm, the carbonization time is 6.5 hours, and the humidity is 70%.
Example 2
A low-carbon gelling material based on low-grade high-magnesium limestone comprises the following preparation raw materials in percentage by mass: 40% of limestone, 28% of calcined clay, 9% of gypsum, 1.5% of aspartic acid, 0.7% of 2-amino terephthalic acid and nano Al 2 O 3 2% and 18.7% of cement clinker.
The preparation method comprises the following steps:
s1, weighing the raw materials according to the mass ratio;
s2, calcining the limestone at 750 ℃ and controlling the decomposition rate of the limestone to be 91.3%;
s3, mixing the calcined product obtained in the step S2 with other raw materials weighed in the step S1: aluminum-silicon material, gypsum, aspartic acid and 2-amino terephthalylFormic acid, nano Al 2 O 3 Mixing the cement clinker uniformly to obtain a primary product;
s4, carbonizing the initial product obtained in the step S3 to obtain the high-performance low-carbon gel material;
wherein, carbonization conditions are: carbonization temperature range 50 ℃, CO 2 The mass concentration range is 10%, the carbonization pressure is 5atm, the carbonization time is 6.5 hours, and the humidity is 70%.
Example 3
A low-carbon gelling material based on low-grade high-magnesium limestone comprises the following preparation raw materials in percentage by mass: 40% of limestone, 28% of calcined clay, 9% of gypsum, 1.2% of aspartic acid, 0.5% of 2-amino terephthalic acid and nano Al 2 O 3 2% and 19.3% of cement clinker.
The preparation method comprises the following steps:
s1, weighing the raw materials according to the mass ratio;
s2, calcining the limestone at 750 ℃ and controlling the decomposition rate of the limestone to be 91.3%;
s3, mixing the calcined product obtained in the step S2 with other raw materials weighed in the step S1: aluminum-silicon material, gypsum, aspartic acid, 2-amino terephthalic acid and nano Al 2 O 3 Mixing the cement clinker uniformly to obtain a primary product;
s4, carbonizing the initial product obtained in the step S3 to obtain the high-performance low-carbon gel material;
wherein, carbonization conditions are: carbonization temperature range 50 ℃, CO 2 The mass concentration range is 10%, the carbonization pressure is 5atm, the carbonization time is 6.5 hours, and the humidity is 70%.
Comparative example 1
This example is substantially the same as example 1, except that:
the preparation raw materials of the cementing material provided by the example comprise the following components in percentage by mass: 40% of limestone, 28% of calcined clay, 9% of gypsum, 2% of aspartic acid and nano Al 2 O 3 2% of cement clinker and 19%.
Comparative example 2
This example is substantially the same as example 1, except that:
the preparation raw materials of the cementing material provided by the example comprise the following components in percentage by mass: 40% of limestone, 28% of calcined clay, 9% of gypsum, 1.2% of 2-amino terephthalic acid and nano Al 2 O 3 2% and 19.8% of cement clinker.
Comparative example 3
This example is substantially the same as example 1, except that:
the preparation raw materials of the cementing material provided by the example comprise the following components in percentage by mass: 40% of limestone, 28% of calcined clay, 9% of gypsum and nano Al 2 O 3 2% of cement clinker and 21%.
Comparative example 4
This example is substantially the same as example 1, except that:
the preparation raw materials of the cementing material provided by the example comprise the following components in percentage by mass: 40% of limestone, 28% of calcined clay, 9% of gypsum, 3.2% of aspartic acid and nano Al 2 O 3 2% and 17.8% of cement clinker.
Comparative example 5
This example is substantially the same as example 1, except that:
the preparation raw materials of the cementing material provided by the example comprise the following components in percentage by mass: 40% of limestone, 28% of calcined clay, 9% of gypsum, 3.2% of 2-amino terephthalic acid and nano Al 2 O 3 2% and 17.8% of cement clinker.
Comparative example 6
This example is substantially the same as example 1, except that: in this example, the decomposition rate of limestone was 4%.
Referring to fig. 1, for the control results of magnesium carbonate crystals by compounding aspartic acid with 2-aminoterephthalic acid, fig. 1, 2 and 3 are scanning electron micrographs of magnesium carbonate crystals obtained by carbonizing MgO without adding aspartic acid and 2-aminoterephthalic acid, only aspartic acid, and with adding aspartic acid and 2-aminoterephthalic acid simultaneously, respectively. Fig. 1 shows that the petal-shaped tri-hydromagnesite content is low, the content in fig. 2 is obviously increased, and fig. 3 shows that the petal-shaped tri-hydromagnesite content and the petal-shaped tri-hydromagnesite content are rich and closely stacked, so that the effect is best, and the aspartic acid and the 2-amino terephthalic acid can be compounded to effectively regulate and control the crystal form of the magnesium carbonate.
The cementing materials of the examples and comparative examples below were prepared as mortar test blocks, reference standards: GB/T17671-1999, tested for 28-day compressive strength, with the test results shown in Table 1 below:
TABLE 1
As can be seen from the results of Table 1, the cement prepared in examples 1 to 3 has excellent compressive strength, and as can be seen from comparative examples 1 to 33, the addition of aspartic acid and 2-amino terephthalic acid has a remarkable enhancement effect on the enhancement of strength, and both of them are poor in effect when used alone, and further by combining comparative examples 4 and 5, it can be fully demonstrated that the synergistic enhancement effect on the enhancement of the cement strength is achieved when the aspartic acid and 2-amino terephthalic acid are added in combination, which is mainly due to the enhancement of MgCO with high solubility by aspartic acid and 2-amino terephthalic acid 3 The content plays a role in synergistic enhancement. As can be seen from comparative example 6, the strength of the cement can be effectively improved by controlling the appropriate decomposition rate of limestone.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. The low-carbon gelling material based on low-grade high-magnesium limestone is characterized by comprising the following preparation raw materials in percentage by mass:
15% -45% of limestone;
20-60% of aluminum-silicon material;
5-10% of gypsum;
aspartic acid 0.5% -3%;
0.5-1.8% of 2-amino terephthalic acid;
nano Al 2 O 3 1.5-14.2％；
13-40% of cement clinker;
the sum of the mass fractions of the raw materials is 100 percent;
wherein the limestone is low-grade high-magnesium limestone with the mass content of magnesium being more than 4 percent.
2. The low-carbon gelling material based on low-grade high-magnesium limestone according to claim 1, wherein the limestone is calcined and decomposed before being used, and the decomposition rate of the limestone is controlled to be 6.7% -92.5%.
3. The low-carbon gelling material of claim 2, wherein the aluminum-silicon material is one or more of calcined clay, mineral powder, relatively high clay, fly ash, gangue, and tailing slurry.
4. A low-carbon gelling material based on low-grade high-magnesium limestone according to claim 3, characterized in that its raw materials for preparation comprise, in mass fraction:
40% of limestone;
28% of an aluminum-silicon material;
gypsum 9%;
aspartic acid 2%;
1.2% of 2-amino terephthalic acid;
nano Al 2 O 3 2％；
The balance of cement clinker;
the sum of the mass fractions of the raw materials is 100 percent.
5. A low-carbon gelling material based on low-grade high-magnesium limestone according to claim 3, characterized in that its raw materials for preparation comprise, in mass fraction:
40% of limestone;
28% of an aluminum-silicon material;
gypsum 9%;
aspartic acid 1.5%;
2-amino terephthalic acid 0.8%;
nano Al 2 O 3 2％；
The balance of cement clinker;
the sum of the mass fractions of the raw materials is 100 percent.
6. The low-carbon gelling material based on low-grade high-magnesium limestone according to claim 4 or 5, wherein the limestone is calcined and decomposed before being used, and the decomposition rate of the limestone is controlled to be 91.3%.
7. A low carbon gelling material based on low-grade high magnesium limestone according to claim 4 or 5, wherein the aluminium siliceous material is a calcined clay.
8. A method for preparing a low carbon gelling material based on low-grade high magnesium limestone according to any one of claims 1-6, comprising the steps of:
s1, weighing the raw materials according to the mass ratio;
s2, calcining the limestone at 710-820 ℃ and controlling the decomposition rate of the limestone to be 6.7-92.5%;
s3, mixing the calcined product obtained in the step S2 with other raw materials weighed in the step S1: aluminum-silicon material, gypsum, aspartic acid, 2-amino terephthalic acid and nano Al 2 O 3 Mixing the cement clinker uniformly to obtain a primary product;
and S4, carbonizing the initial product obtained in the step S3 to obtain the high-performance low-carbon gel material.
9. The method for preparing a low-carbon gelling material based on low-grade high-magnesium limestone as claimed in claim 8, whereinCharacterized in that the carbonization conditions in the step S4 are as follows: carbonization temperature range of 20-80 ℃, CO 2 The mass concentration range is 5-20%, the carbonization pressure is 1-10atm, the carbonization time is 5-8 hours, and the humidity is 50-90%.
10. The method for preparing a low-carbon gelling material based on low-grade high-magnesium limestone according to claim 9, comprising the steps of:
s1, weighing the raw materials according to the mass ratio;
s2, calcining the limestone at 750 ℃ and controlling the decomposition rate of the limestone to be 91.3%;
s3, mixing the calcined product obtained in the step S2 with other raw materials weighed in the step S1: aluminum-silicon material, gypsum, aspartic acid, 2-amino terephthalic acid and nano Al 2 O 3 Mixing the cement clinker uniformly to obtain a primary product;
s4, carbonizing the initial product obtained in the step S3 to obtain a high-performance low-carbon gel material;
wherein, carbonization conditions are: carbonization temperature range 50 ℃, CO 2 The mass concentration range is 10%, the carbonization pressure is 5atm, the carbonization time is 6.5 hours, and the humidity is 70%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108430945A (en) * | 2015-11-16 | 2018-08-21 | Gcp应用技术有限公司 | Quick lime aquation delays to start |
| CN110683780A (en) * | 2019-09-03 | 2020-01-14 | 浙江大学 | Modified fly ash for curing and sealing carbon dioxide and preparation method thereof |
| CN111925141A (en) * | 2020-07-25 | 2020-11-13 | 大同冀东水泥有限责任公司 | Method for preparing cement clinker from high-magnesium high-soda limestone |
| CN115231837A (en) * | 2022-07-13 | 2022-10-25 | 兰溪南方水泥有限公司 | 32.5 low-alkali masonry cement with large-doping amount and low-grade limestone and preparation method thereof |
| CN115677243A (en) * | 2022-12-08 | 2023-02-03 | 中国建筑材料科学研究总院有限公司 | Novel low-carbon cement clinker and preparation method thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108430945A (en) * | 2015-11-16 | 2018-08-21 | Gcp应用技术有限公司 | Quick lime aquation delays to start |
| CN110683780A (en) * | 2019-09-03 | 2020-01-14 | 浙江大学 | Modified fly ash for curing and sealing carbon dioxide and preparation method thereof |
| CN111925141A (en) * | 2020-07-25 | 2020-11-13 | 大同冀东水泥有限责任公司 | Method for preparing cement clinker from high-magnesium high-soda limestone |
| CN115231837A (en) * | 2022-07-13 | 2022-10-25 | 兰溪南方水泥有限公司 | 32.5 low-alkali masonry cement with large-doping amount and low-grade limestone and preparation method thereof |
| CN115677243A (en) * | 2022-12-08 | 2023-02-03 | 中国建筑材料科学研究总院有限公司 | Novel low-carbon cement clinker and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 焦有宙;李慧灵;赵迎芳;张全国;: "粉煤灰与低品位石灰石制备Q相水泥熟料的试验研究", 实验技术与管理, no. 03, 20 March 2009 (2009-03-20), pages 53 - 57 * |
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