CN117447108A - Composite cementing material and preparation method thereof - Google Patents
Composite cementing material and preparation method thereof Download PDFInfo
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- CN117447108A CN117447108A CN202311393421.0A CN202311393421A CN117447108A CN 117447108 A CN117447108 A CN 117447108A CN 202311393421 A CN202311393421 A CN 202311393421A CN 117447108 A CN117447108 A CN 117447108A
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 41
- 239000010802 sludge Substances 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000002734 clay mineral Substances 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 5
- 239000010433 feldspar Substances 0.000 claims description 5
- 150000003841 chloride salts Chemical class 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 28
- 230000036571 hydration Effects 0.000 abstract description 10
- 238000006703 hydration reaction Methods 0.000 abstract description 10
- 239000002910 solid waste Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 7
- 230000004907 flux Effects 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000000274 adsorptive effect Effects 0.000 abstract 1
- 230000005284 excitation Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000004568 cement Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000000404 calcium aluminium silicate Substances 0.000 description 2
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 2
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 2
- 229940078583 calcium aluminosilicate Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000003334 potential effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KYLIZBIRMBGUOP-UHFFFAOYSA-N Anetholtrithion Chemical group C1=CC(OC)=CC=C1C1=CC(=S)SS1 KYLIZBIRMBGUOP-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 monothio Chemical group 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention relates to the technical field of building materials, in particular to a composite cementing material and a preparation method thereof. The raw materials of the composite cementing material comprise 40-55 parts of carbide slag, 70-80 parts of seabed sludge, 10-20 parts of gamma-alumina and 15-20 parts of exciting agent in parts by weight. The invention simultaneously utilizes the carbide slag and the seabed sludge to realize the cooperative treatment of various solid wastes. In the preparation process, the gel material achieves high hydration activity through combined excitation of heat, machinery and chemistry, and the system is promoted to produce more high Cl through the directional design of hydration products ‑ Adsorptive product, realize to Cl ‑ Is solid-dissolved in situ. The composite cementing material provided by the invention is suitable for producing concrete with different strength grades, has excellent adaptability and low electric flux, and shows good chloride ion permeation resistance.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a composite cementing material and a preparation method thereof.
Background
Various solid wastes are accumulated gradually, and a huge threat is formed to the ecological environment. Of these, carbide slag and marine sludge are two very representative ones.
The carbide slag is solid waste generated after acetylene gas is prepared from calcium carbide, and is one of main waste generated in the high-end petrochemical industry. The carbide slag contains trace carbon and sulfur impurities, is gray, has slight odor and is strong alkaline. At present, the reuse of carbide slag is often represented by using carbide slag as a production building material, chemical product or treating waste water, waste gas, etc. However, the added value and economic benefit of the products produced by the treatment methods are low, and the amount of the consumed carbide slag is limited, so that a large amount of carbide slag is still piled up or buried in the open air. The outdoor stacking or burying treatment mode not only occupies a large amount of land resources, but also can pollute the soil to alkalize the soil due to lack of anti-seepage treatment measures in the stacking and burying process; serious erosion to air, surface water and groundwater is generated; meanwhile, the carbide slag dust particles fly along with wind to cause serious pollution to the environment, and the normal life and physical health condition of the living community are endangered.
The seabed sludge is a natural solid waste formed by long-term erosion of seabed in natural conditions such as water flow erosion, ecological evolution and the like. In recent years, as we build up infrastructures such as ports and wharfs, the problem of sea mud accumulation is more serious, and treatment is needed. At present, the treatment modes of the seabed sludge are mainly four, one is to prepare the baked brick by using the seabed sludge, but the problems of salt impregnation, poor surface cohesiveness and the like of the baked brick are easily caused by a large amount of salt in the seabed sludge; secondly, preparing solidified soil by utilizing seabed sludge, wherein the components in sea sludge are complex and changeable, and the prepared solidified soil is unstable in quality; thirdly, a small amount of submarine sludge is used as a concrete mineral admixture, but the submarine sludge has low volcanic ash activity and is rich in chloride ions, so that the durability risk of the concrete is easily induced; fourthly, the seabed sludge is transported to a position far away from the shore to be thrown, but the method can have a great influence on the local environment.
In summary, the prior art still has the defects of various solid wastes, especially the treatment means of carbide slag and seabed sludge, and further causes environmental pollution. Based on this, there is a need in the art for a method that utilizes both carbide slag and subsea sludge to achieve the co-disposal of multiple solid wastes.
Disclosure of Invention
The invention aims to provide a composite cementing material and a preparation method thereof, and simultaneously, the method of carbide slag and seabed sludge is utilized to realize the cooperative treatment of various solid wastes.
In order to achieve the above object, the present invention provides the following technical solutions:
the composite cementing material is prepared from the following raw materials in parts by weight:
optionally, the particle size of the seabed sludge is smaller than 150 mu m, and the seabed sludge comprises 40-55% of quartz, 20-25% of clay mineral, 15-25% of ground matter, 3-15% of organic matter and the balance of erosive inorganic salt according to mass percent;
the organic matter comprises CaCO 3 And feldspar;
the aggressive inorganic salts comprise chloride salts and sulfate salts.
Optionally, the particle size of the carbide slag is less than 100 μm; the particle size of the gamma alumina is less than 100nm.
Optionally, the activator comprises sodium carbonate and sodium hydroxide.
Optionally, the mass ratio of sodium carbonate to sodium hydroxide in the excitant is 1:1.5 to 2.5.
The invention also provides a preparation method of the composite cementing material, which comprises the following steps:
1) Mixing carbide slag, seabed sludge and gamma-alumina as materials;
2) Calcining the material in the step 1);
3) Grinding the calcined material obtained in the step 2);
4) Mixing the ground material in the step 3) with an exciting agent to obtain the composite cementing material.
Optionally, the calcining temperature in the step 2) is 750-1000 ℃, and the calcining time is 45-90 min.
Optionally, the grinding in the step 3) is to grind the calcined material to a specific surface area of 350-450 m 2 /kg。
From the aspect of element correction, the seabed sludge contains a large amount of siliceous and aluminous components, and the contained clay components have larger potential activities, so that the potential activities are reasonably released through scientific means. The carbide slag can be used as a high-calcium solid waste and can be used as an excellent calcium correction productThe CaO-Al composite material can be reasonably constructed for a system 2 O 3 -SiO 2 A ternary system. The system products are guided directionally by other small amount of ionic compounds, so that the synergistic improvement of high hydration activity and low durability risk is realized.
The invention takes carbide slag as a main calcium source, seabed sludge as a main silicon source, nano alumina as a main aluminum source, and uses an excitant obtained by compounding sodium carbonate and sodium hydroxide to supplement a certain amount of carbonate ions, so as to directionally guide hydration products to generate hydrotalcite phases and calcium aluminosilicate gel. The hydrotalcite phase can largely adsorb Cl by interlayer ion exchange - 、SO 4 2- . The generated calcium aluminosilicate gel not only has higher cementation performance, but also has larger specific surface area, and can provide more Cl - Adsorption point positions. In addition, the designed high-aluminum system can be used for converting harmful ions SO existing in the system 4 2- Converted into trithio hydrated calcium sulfoaluminate (AFt), monothio hydrated calcium sulfoaluminate (AFm), and further combined with Cl - F salt is generated, so that the gel material is endowed with higher hydration activity, and meanwhile, harmful elements in sea mud are strongly adsorbed, and the generation of durability risks is avoided.
In the invention, inert substances in raw materials are modified through thermal-mechanical-chemical coupling treatment, so that the purpose of high activity is achieved, and excellent physical and chemical properties are provided for the cementing material;
the clay minerals in the sea mud are calcined to remove hydroxyl groups, so that certain hydration activity is generated. At the same time, in the heat activation, mechanical activation and Ca 2+ Under the polarization effect of the quartz glass, a large amount of quartz components in the raw materials can better complete the vitrification process. Al (Al) 2 O 3 On the one hand, the silicon chain can be inserted to prevent the silicon chain from repolymerization, and compared with the current traditional activation method, the silicon chain has higher dismembering degree and is formed by Q 4 To Q 0 The conversion is more thorough, so that the hydration activity of the cementing material is further improved.
Compared with the prior art, the invention has the following beneficial effects:
the main raw materials of the carbide slag/sea mud-based composite cementing material provided by the invention are industrial solid wastes, so that the cooperative treatment of 'treating wastes with wastes' and various solid wastes is realized, and the social environmental benefit is remarkable;
according to the invention, through reasonable ingredients, the hydration product of the cementing material is regulated and designed, so that the in-situ solid solution of aggressive substances such as chloride salt, sulfate and the like in the cementing material system is realized, and the durability threat to a final product is avoided;
the composite cementing material provided by the invention is suitable for producing concrete with different strength grades, has excellent adaptability and low 28d electric flux, and shows good chloride ion permeation resistance;
the preparation method of the carbide slag/sea mud-based composite cementing material is simple and feasible, and has industrial value.
Detailed Description
The invention provides a composite cementing material which is prepared from the following raw materials in parts by weight:
in the present invention, the weight parts of the carbide slag may preferably be 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts;
the particle size of the carbide slag is less than 100 μm, preferably less than 95 μm, more preferably 90 μm, still more preferably 80 μm;
the carbide slag contains 85-95% Ca (OH) by mass percent 2 、1～10％CaCO 3 1-3% of unreacted carbon particles and the balance of silicon-containing compounds;
ca (OH) in carbide slag 2 The content of (2) is preferably 87 to 93%, more preferably 88 to 92%, still more preferably 89 to 90%;
CaCO in carbide slag 3 The content of (2) is preferably 2 to 8%, more preferably 4 to 7%, still more preferably 5 to 6%;
the content of unreacted carbon particles in the carbide slag is preferably 1 to 2%, more preferably 1.5 to 1.7%.
In the present invention, the weight parts of the subsea sludge may preferably be 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts;
the particle size of the subsea sludge is less than 150 μm, preferably less than 140 μm, more preferably less than 130 μm, still more preferably less than 120 μm;
the seabed sludge comprises, by mass, 40-55% of quartz, 20-25% of clay minerals, 15-25% of ground substances, 3-15% of organic matters and the balance of aggressive inorganic salts;
the organic matter comprises CaCO 3 And feldspar;
the aggressive inorganic salts comprise chloride salts and sulfate salts;
the quartz in the seabed sludge is preferably 44-52%, more preferably 44.3-50%, even more preferably 45-48%;
the clay mineral is preferably 21 to 24%, more preferably 22 to 23%, still more preferably 22.3 to 22.5%;
the geologic material is preferably 16 to 24%, more preferably 18 to 21%, still more preferably 19 to 20%; the geological matter comprises CaCO with arbitrary proportion 3 And feldspar, and CaCO 3 And feldspar are not 0 at the same time;
the organic matter is preferably 5 to 13%, more preferably 9 to 12.5%, still more preferably 10 to 12%;
the aggressive inorganic salts comprise chloride and sulfate salts in any proportion.
In the present invention, the weight part of the gamma alumina is preferably 12 to 19 parts, more preferably 14 to 18 parts, still more preferably 15 to 16 parts;
the particle size of the gamma-alumina is less than 100nm, preferably less than 90nm, more preferably less than 80nm, and even more preferably less than 70nm.
In the present invention, the weight part of the activator is preferably 16 to 19 parts, more preferably 17 to 18 parts;
the excitant comprises sodium carbonate and sodium hydroxide;
the mass ratio of sodium carbonate to sodium hydroxide in the excitant is 1:1.5 to 2.5, preferably 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4.
the invention also provides a preparation method of the composite cementing material, which comprises the following steps:
1) Mixing carbide slag, seabed sludge and gamma-alumina as materials;
2) Calcining the material in the step 1);
3) Grinding the calcined material obtained in the step 2);
4) Mixing the ground material in the step 3) with an exciting agent to obtain the composite cementing material.
In the present invention, the temperature of the calcination in step 2) is 750 to 1000 ℃, preferably 800 to 950 ℃, and more preferably 850 to 900 ℃;
the calcination time is 45 to 90 minutes, preferably 50 to 80 minutes, more preferably 55 to 70 minutes, still more preferably 60 to 65 minutes;
the grinding step 3) is to grind the calcined material to a specific surface area of 350-450 m 2 Preferably 360 to 446m per kg 2 Preferably 380 to 420m per kg 2 Per kg, more preferably 387 to 400m 2 /kg；
The mixing in step 1) and step 4) may be accomplished by mixing in a planetary ball mill for a period of 7 to 15 minutes, preferably 8 to 13 minutes, more preferably 9 to 12 minutes, and even more preferably 10 to 11 minutes.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking carbide slag and seabed sludge as raw materials.
The carbide slag comprises 90.4% Ca (OH) by mass percent 2 、7.0％CaCO 3 1.7% unreacted carbon particlesThe balance of silicon-containing compound;
the seabed sludge comprises, by mass, 44.3% of quartz, 22.3% of clay minerals, 19.0% of ground substances, 12.5% of organic substances and the balance of aggressive inorganic salts.
55 parts of carbide slag, 70 parts of seabed sludge and 15 parts of gamma-alumina are weighed and uniformly mixed in a planetary ball mill to be used as materials, and then the materials are calcined at 900 ℃ for 1h, and are rapidly cooled by an air cooling machine. Grinding the cooled material to a specific surface area of 387m 2 15 parts of a sodium carbonate and sodium hydroxide composite material are subsequently added as an activator, wherein the mass ratio of sodium carbonate to sodium hydroxide is 1: and 2, uniformly mixing to obtain the carbide slag/sea mud-based composite cementing material A.
Example 2
The composition of the carbide slag and the seabed sludge is the same as that of the embodiment 1;
40 parts of carbide slag, 80 parts of seabed sludge and 20 parts of gamma-alumina are weighed and uniformly mixed in a planetary ball mill to be used as materials, and then the materials are calcined at 900 ℃ for 1h, and are rapidly cooled by an air cooling machine. Grinding the cooled material to a specific surface area of 446m 2 20 parts of a sodium carbonate and sodium hydroxide composite material are subsequently added as an activator, wherein the mass ratio of sodium carbonate to sodium hydroxide is 1: and 1.5, uniformly mixing to obtain the carbide slag/sea mud-based composite cementing material B.
Application examples 1 to 2
Mortar was prepared using the carbide slag/sea mud-based composite cement material a prepared in example 1 and the carbide slag/sea mud-based composite cement material B prepared in example 2, respectively, and the strength grade of the mortar was determined with reference to GB/T175-2007 cement standard vibration and test analysis standard.
Table 1 standard mortar prepared from composite cement A, B and its compressive strength
As shown in Table 1, the 28d compressive strength of the standard mortar test pieces prepared in application examples 1 and 2 is 49.2MPa and 51.1MPa respectively, and is greater than 42.5MPa, and the compressive strength requirement of the standard mortar test pieces for 42.5-grade ordinary Portland cement in relevant regulations is met, so that the carbide slag/sea mud-based composite cementing material disclosed by the invention is excellent in hydration activity and can be used for preparing mortar.
Application examples 3 to 6
Concrete of grade C30 and C60 was prepared by using the carbide slag/sea mud based composite cementing materials A, B prepared in examples 1-2, respectively, and the formulations used are shown in Table 2.
Table 2 formulations/kg for preparing concrete according to application examples 3 to 6
Comparative examples 1 to 2
The concrete with the grade of C30 and C60 is prepared by using the commercial P.O42.5R cement. The specific formulation is shown in table 3.
TABLE 3 formulation/kg of commercial P.O 42.5R Cement to concrete
| Numbering device | Concrete grade | Cement and its preparation method | Mineral powder | Fly ash | Sand and sand | Stone | Water and its preparation method | Additive agent |
| Comparative example 1 | C30 | 200 | 80 | 60 | 810 | 1040 | 160 | 8.8 |
| Comparative example 2 | C60 | 380 | 100 | 80 | 640 | 1050 | 150 | 15.1 |
The compressive strength of the concrete prepared in application examples 3 to 6 and comparative examples 1 to 2 was measured with reference to GB/T50081-2019 Standard for test method of physical mechanical Properties of concrete, and the chloride ion resistance of the concrete prepared in application examples 3 to 6 and comparative examples 1 to 2 was measured with reference to GB/T50082-2009 Standard for test method of long-term Performance and durability of ordinary concrete, and the results are shown in Table 4.
Table 4 Properties of the concrete obtained as a result of the comparative test of examples 3 to 6 and comparative examples 1 to 2
The C30 grade concrete is concrete with the compressive strength grade of 30 MPa. As can be seen from Table 4, the 28d compressive strength of the concrete prepared in application examples 3 and 4 was 35.8MPa and 34.1MPa, respectively, which all satisfied the strength requirements of C30 grade concrete. The 28d electric flux of the C30 concrete prepared in application examples 3 to 4 was significantly smaller than that of the commercial C30 concrete shown in comparative document 1, compared with comparative example 1.
The C60 grade concrete is a concrete with a compressive strength grade of 60MPa, and as can be seen from Table 4, the 28d compressive strengths of the concrete prepared in application examples 5 and 6 are 68.8MPa and 64.2MPa, respectively, which satisfy the strength requirements of the C60 grade concrete. The 28d electric flux of the concretes produced in examples 5 to 6 is significantly less than that of the commercial C60 commercial concrete compared with comparative example 2.
According to the embodiment, the carbide slag/sea mud based composite cementing material provided by the invention has excellent adaptability to materials such as market main flowing sand, stone and additives, and can be used for preparing a concrete material with lower 28d electric flux and excellent chloride ion resistance. And the hydration product contains hydrotalcite and aluminosilicate phase, so that a large amount of chloride ions in sea mud and outside invasion can be adsorbed, and the anti-chloride ion performance is excellent. Therefore, the carbide slag/sea mud based composite cementing material provided by the invention can be widely applied to the production of concrete with different strength grades, and has a huge application prospect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The composite cementing material is characterized by being prepared from the following raw materials in parts by weight:
2. the composite cementing material according to claim 1, wherein the particle size of the seabed sludge is less than 150 μm, and the seabed sludge comprises 40-55% of quartz, 20-25% of clay mineral, 15-25% of ground matter, 3-15% of organic matter and the balance of corrosive inorganic salt in percentage by mass;
the organic matter comprises CaCO 3 And feldspar;
the aggressive inorganic salts comprise chloride salts and sulfate salts.
3. A composite cementitious material according to claim 1 or 2, wherein the carbide slag has a particle size of less than 100 μm; the particle size of the gamma alumina is less than 100nm.
4. A composite cementitious material according to claim 1 or 2, wherein the activator comprises sodium carbonate and sodium hydroxide.
5. The composite cementing material according to claim 4, wherein the mass ratio of sodium carbonate to sodium hydroxide in the excitant is 1:1.5 to 2.5.
6. A method for preparing a composite cementitious material as defined in any one of claims 1 to 5, comprising the steps of:
1) Mixing carbide slag, seabed sludge and gamma-alumina as materials;
2) Calcining the material in the step 1);
3) Grinding the calcined material obtained in the step 2);
4) Mixing the ground material in the step 3) with an exciting agent to obtain the composite cementing material.
7. The method for preparing a composite cementing material according to claim 6, wherein the calcining temperature in step 2) is 750-1000 ℃ and the calcining time is 45-90 min.
8. The method for preparing a composite cementitious material according to claim 6 or 7, wherein the grinding in step 3) is grinding the calcined material to a specific surface area of 350-450 m 2 /kg。
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