CN115196893A - Corrosion-resistant marine cement and preparation method thereof - Google Patents
Corrosion-resistant marine cement and preparation method thereof Download PDFInfo
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- CN115196893A CN115196893A CN202210924957.XA CN202210924957A CN115196893A CN 115196893 A CN115196893 A CN 115196893A CN 202210924957 A CN202210924957 A CN 202210924957A CN 115196893 A CN115196893 A CN 115196893A
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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
- C04B7/00—Hydraulic cements
- C04B7/02—Portland cement
- C04B7/06—Portland cement using alkaline raw materials
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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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
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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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses corrosion-resistant marine cement and a preparation method thereof, wherein the cement comprises the following components in percentage by weight: 6-30% of tetracalcium aluminoferrite; 2-10% of fly ash; 2-10% of silica fume; 3-15% of limestone powder; 5-25% of coal gangue powder loaded with carbon nanotubes; the balance being cement clinker. According to the corrosion-resistant marine cement provided by the invention, the corrosion resistance and durability of a cement-based material can be remarkably improved by introducing the multi-wall carbon nano tube loaded by the porous high-alumina coal gangue powder into the cement, so that the cement is more suitable for being used in a marine environment; the porous high-aluminum coal gangue powder is used as a carrier to load the multi-walled carbon nano-tubes, so that the defect that the multi-walled carbon nano-tubes are easy to agglomerate can be well overcome, and the multi-walled carbon nano-tubes can be uniformly dispersed into a cement system; meanwhile, the hole-activated high-alumina coal gangue powder also introduces a large amount of alumina in a cement system,can form more AH 3 The aluminum cement improves the compactness and the erosion resistance of a cement hydration sample.
Description
Technical Field
The invention relates to the field of cement materials, in particular to corrosion-resistant marine cement and a preparation method thereof.
Background
As a main material of ocean engineering, the durability of cement-based materials in a seawater environment is an inevitable problem, and the resistance to the penetration of chloride ions, sulfate erosion and the like in the seawater environment is a problem to be solved when concrete is used in the ocean environment. The durability of cement as a concrete binder in a seawater environment directly determines the durability of concrete.
Portland cement is a basic raw material in the building industry in China and has wide application, but the problem that the Portland cement is easily corroded by sulfate and chloride ions is still a main reason for limiting the use of the Portland cement in a seawater environment. The corrosion of sulfate and the penetration of chloride ions can cause the peeling corrosion of cement and the corrosion of steel bars in concrete, so that the strength of an engineering structure is reduced, and the service life is shortened.
Therefore, there is a need to develop corrosion resistant cements suitable for use in marine environments.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the corrosion-resistant marine cement and the preparation method thereof aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that: the corrosion-resistant marine cement comprises the following components in percentage by weight:
preferably, the cement clinker is portland cement clinker.
Preferably, the carbon nanotube-loaded coal gangue powder is obtained by loading multi-wall carbon nanotubes on porous high-aluminum coal gangue powder, and the specific preparation method comprises the following steps:
1) Preparing porous activated high-alumina coal gangue powder by using high-alumina coal gangue;
2) Preparing a modified multi-walled carbon nanotube solution;
3) The coal gangue powder loaded with the carbon nano tubes is prepared by utilizing porous activated high-aluminum coal gangue powder and a modified multi-wall carbon nano tube solution.
Preferably, the step 1) specifically includes:
1-1) preparing porous high-aluminum coal gangue powder:
1-1-1) grinding the high-alumina coal gangue to a content of less than 200 meshes which is more than 95 percent to obtain coal gangue powder;
1-1-2) mixing the coal gangue powder and the aluminum powder, uniformly stirring, adding water, and reacting under continuous stirring;
1-1-3) drying and roasting the product obtained in the step 1-1-2) under stirring, and crushing the product to obtain porous high-aluminum coal gangue powder;
1-2) carrying out activation modification on the high-alumina coal gangue powder to prepare porous high-alumina coal gangue powder:
dispersing the porous high-aluminum coal gangue powder obtained in the step 1-1) into ethanol, adding gamma-aminopropyl triethoxysilane, ultrasonically dispersing, reacting under the conditions of heating and continuous stirring, centrifuging after the reaction is finished, cleaning a solid product, then adding the solid product into water, and stirring the solid product into a slurry state to obtain slurry of the porous activated high-aluminum coal gangue powder for later use.
Preferably, the step 1) specifically includes:
1-1) preparing porous high-aluminum coal gangue powder:
1-1-1) grinding the high-alumina coal gangue to a content of less than 200 meshes which is more than 95 percent to obtain coal gangue powder;
1-1-2) mixing the coal gangue powder with a foaming agent, uniformly stirring, adding water, and reacting for 3-8h under continuous stirring;
1-1-3) drying the product obtained in the step 1-1-2) under stirring, then roasting for 4-10h at 700-950 ℃, and crushing the product to obtain porous high-aluminum coal gangue powder;
1-2) carrying out activation modification on the high-aluminum coal gangue powder to prepare porous high-aluminum coal gangue powder:
dispersing the porous high-aluminum coal gangue powder obtained in the step 1-1) into ethanol, adding gamma-aminopropyl triethoxysilane, ultrasonically dispersing for 0.5-2h, reacting for 3-8h at 80-115 ℃ under continuous stirring, centrifuging, cleaning a solid product, then adding the solid product into water, and stirring into a slurry state to obtain slurry of the porous activated high-aluminum coal gangue powder for later use.
Preferably, the step 2) specifically includes: adding a multi-walled carbon nano tube into mixed acid of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic dispersion, reacting under a heating condition, and after the reaction is finished, separating out a solid product and washing;
and adding the solid product into hydrofluoric acid, soaking, adding ammonia water into the mixed solution, stirring for reaction until the pH value of the solution is 6.5-7, and stopping the reaction to obtain a modified multi-walled carbon nanotube solution for later use.
Preferably, the step 2) specifically includes: adding the multi-walled carbon nano-tube into mixed acid of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic dispersion for 15-60min, reacting for 0.5-3h at 75-100 ℃, separating out a solid product and washing;
and adding the solid product into hydrofluoric acid, soaking for 6-24 hours, adding ammonia water into the mixed solution, stirring for reaction until the pH value of the solution is 6.5-7, and stopping the reaction to obtain a modified multi-walled carbon nanotube solution for later use.
Preferably, the step 3) specifically includes: adding the modified multi-walled carbon nanotube solution obtained in the step 2) into the slurry of the porous activated high-aluminum coal gangue powder obtained in the step 1) under stirring, reacting for 2-10h under continuous stirring, drying in vacuum, and crushing the product to obtain the coal gangue powder loaded with the carbon nanotubes.
Preferably, in the high-aluminum coal gangue powder, al is contained 2 O 3 The mass percentage content is more than 28 percent.
Preferably, the preparation method of the corrosion-resistant marine cement comprises the following steps:
s1, mixing tetracalcium aluminoferrite, fly ash, silica fume, limestone powder and carbon nanotube-loaded coal gangue powder according to weight ratio, and grinding;
s2, uniformly mixing the mixed powder obtained in the step 1) with silicate cement clinker to obtain the corrosion-resistant marine engineering cement.
The invention has the beneficial effects that:
according to the corrosion-resistant marine cement provided by the invention, the multi-walled carbon nano tube loaded by the porous high-aluminum gangue powder is introduced into the cement, so that the corrosion resistance and durability of the cement-based material can be obviously improved, and the cement is more suitable for being used in a marine environment;
according to the invention, the high-aluminum coal gangue is used as a raw material, the porous activated high-aluminum coal gangue powder modified with amino functional groups is prepared, and the multi-wall carbon nano tube can be well loaded; according to the invention, a large amount of oxygen-containing groups such as-OH, -C = O, -COOH and the like are introduced on the surface of the multi-walled carbon nanotube, then the multi-walled carbon nanotube is connected and loaded on the porous activated high-alumina coal gangue powder by utilizing the action of a bond bridge, and finally a multi-walled carbon nanotube-porous activated high-alumina coal gangue powder structural system is formed, and the multi-walled carbon nanotube is loaded by adopting the porous high-alumina coal gangue powder as a carrier, so that the defect that the multi-walled carbon nanotube is easy to agglomerate can be well overcome, the multi-walled carbon nanotube can be uniformly dispersed in a cement system, and the functions of improving the corrosion resistance and the durability of the cement can be fully exerted; meanwhile, the pore-activated high-alumina coal gangue powder introduces a large amount of alumina in a cement system, and can inhibit a cement hydration product tricalcium aluminate (C) from hydrating in the cement hydration process 3 AH 6 ) On the other hand, more AH will be formed 3 The aluminum cement slows down the increase of porosity caused by hydration shrinkage of cement, and improves the hydration density and the erosion resistance of the cement. Therefore, the corrosion resistance and durability of the cement can be greatly improved by means of the dual functions of the porous high-aluminum gangue powder carrier and the multi-walled carbon nano tube loaded on the porous high-aluminum gangue powder carrier.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference 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 invention provides corrosion-resistant marine cement which comprises the following components in percentage by weight:
wherein the cement clinker is silicate cement clinker. Al in high-alumina gangue powder 2 O 3 The mass percentage content is more than 28 percent.
The coal gangue powder loading the carbon nanotubes is obtained by loading the multiwalled carbon nanotubes on porous high-aluminum coal gangue powder, and the specific preparation method comprises the following steps:
1) Preparing porous activated high-aluminum coal gangue powder by using high-aluminum coal gangue:
1-1) preparing porous high-aluminum coal gangue powder:
1-1-1) grinding the high-alumina coal gangue to a content of less than 200 meshes which is more than 95 percent to obtain coal gangue powder;
1-1-2) mixing the coal gangue powder with a foaming agent, uniformly stirring, adding water, and reacting for 3-8h under continuous stirring; in the embodiment, the foaming agent is aluminum powder;
1-1-3) drying the product obtained in the step 1-1-2) under stirring, then roasting for 4-10h at 700-950 ℃, and crushing the product to obtain porous high-aluminum coal gangue powder;
1-2) carrying out activation modification on the high-alumina coal gangue powder to prepare porous high-alumina coal gangue powder:
dispersing the porous high-aluminum coal gangue powder obtained in the step 1-1) into ethanol, adding a coupling agent KH550 (gamma-aminopropyltriethoxysilane), ultrasonically dispersing for 0.5-2h, reacting for 3-8h under continuous stirring at 80-115 ℃, centrifuging, cleaning a solid product, adding into water, and stirring into a slurry state to obtain slurry of the porous activated high-aluminum coal gangue powder for later use.
2) Preparing a modified multi-walled carbon nanotube solution:
the step 2) specifically comprises the following steps: adding the multi-walled carbon nano-tube into mixed acid of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic dispersion for 15-60min, reacting for 0.5-3h at 75-100 ℃, separating out a solid product and washing;
and adding the solid product into hydrofluoric acid (10-45%), soaking for 6-24 hours, adding ammonia water into the mixed solution, stirring for reaction until the pH value of the solution is 6.5-7, and stopping the reaction to obtain a modified multi-wall carbon nanotube solution for later use.
3) Preparing the coal gangue powder loaded with the carbon nano tubes by using porous activated high-aluminum coal gangue powder and a modified multi-walled carbon nano tube solution:
adding the modified multi-walled carbon nanotube solution obtained in the step 2) into the slurry of the porous activated high-aluminum coal gangue powder obtained in the step 1) under stirring, reacting for 2-10h under continuous stirring, drying in vacuum, and crushing the product to obtain the coal gangue powder loaded with the carbon nanotubes. In the coal gangue powder material loading the carbon nano-tubes, the mass content of the multi-wall carbon nano-tubes is 0.5-10%.
The invention also provides a preparation method of the corrosion-resistant marine cement, which comprises the following steps:
s1, mixing tetracalcium aluminoferrite, fly ash, silica fume, limestone powder and coal gangue powder loaded with carbon nanotubes according to a weight ratio, and grinding;
s2, uniformly mixing the mixed powder obtained in the step 1) with silicate cement clinker to obtain the corrosion-resistant marine engineering cement.
The erosion effects on cement in marine environments mainly include: 1. high-content chloride ions erode to increase the solubility of hydrate, decompose cement hydration products and destroy the strength of cement; 2. erosion action of high content of sulfate ions.
In the invention, the corrosion resistance and durability of the cement-based material can be obviously improved by introducing the multi-walled carbon nanotubes into the cement, so that the cement-based material is more suitable for being used in a marine environment, and the specific reasons are as follows:
the multi-walled carbon nanotube has various advantages of nano materials and carbon materials, such as high strength, good toughness, corrosion resistance, large specific surface area, compact structure and the like, and can be doped into cement, on one hand, the generation amount of early hydration products of the cement-based materials can be enhanced through nano filling and nucleation effects, the content of high-density hydrated calcium silicate is increased, the early self-shrinkage of the materials is inhibited, the generation of microcracks is reduced, the void ratio and the pore diameter of the cement-based materials are optimized, so that the cement-based materials have a more compact microstructure, and the chloride ion and sulfate ion permeation resistance of the cement-based materials can be improved; on the other hand, the multi-wall carbon nano-tube plays a role in coupling, so that the microstructure of the cement-based material can be improved, and the durability is improved.
Then, the multi-walled carbon nanotubes are easy to agglomerate due to the strong van der waals force among the multi-walled carbon nanotubes, so that the multi-walled carbon nanotubes cannot be uniformly dispersed in a material system, and the application of the multi-walled carbon nanotubes in cement is greatly limited. According to the invention, the porous high-alumina coal gangue powder is used as a carrier to load the multi-walled carbon nanotubes, so that the defect can be well overcome, the multi-walled carbon nanotubes can be uniformly dispersed in a cement system, and the functions of improving the corrosion resistance and the durability of the cement are fully exerted. Meanwhile, the load structure introduces a large amount of alumina into a cement system, and can inhibit a cement hydration product tricalcium aluminate (C) from hydrating in the cement hydration process 3 AH 6 ) And also more AH will be formed 3 The aluminum cement slows down the increase of porosity caused by cement hydration shrinkage, and improves the hydration density and the erosion resistance of cement. Therefore, the corrosion resistance and durability of the cement can be greatly improved by means of the dual functions of the porous high-aluminum gangue powder carrier and the multi-walled carbon nano tube loaded on the porous high-aluminum gangue powder carrier.
Specifically, in the invention, high-aluminum coal gangue powder and foaming agent aluminum powder are firstly added into water, the high-aluminum coal gangue powder forms a large amount of micropore structures by virtue of gas generated in the reaction process, and then high-Al is obtained by roasting 2 O 3 The porous high-aluminum coal gangue powder comprises the following main reactions:
2Al+6H 2 O→Al(OH) 3 ↓+3H 2 ↑；
4Al+3O 2 →2Al 2 O 3 ；
2Al(OH) 3 →Al2O 3 +3H 2 O↑。
and (3) eroding the high-alumina gangue powder to form a large amount of fine pore structures under the action of strong gas generated by reaction to obtain the porous high-alumina gangue powder. And then, activating and modifying the porous high-aluminum coal gangue powder by using gamma-aminopropyltriethoxysilane, and introducing amino functional groups into the surface and pores of the porous high-aluminum coal gangue powder to obtain the porous activated high-aluminum coal gangue powder so as to load the multi-wall carbon nano tube.
According to the invention, the multi-walled carbon nanotube is firstly soaked and acidified in mixed acid of concentrated sulfuric acid and concentrated nitric acid and hydrofluoric acid, a large number of oxygen-containing groups such as-OH, -C = O, -COOH and the like are introduced to the surface of the multi-walled carbon nanotube, so that the polarity of the multi-walled carbon nanotube in water can be enhanced, the dispersing capacity is improved, and meanwhile, the functional groups can be used as connecting sites to be connected with amino functional groups on porous activated high-alumina gangue powder, so that the multi-walled carbon nanotube can be connected and loaded on the porous activated high-alumina gangue powder in a large amount, and finally a multi-walled carbon nanotube-porous activated high-alumina gangue powder structural system is formed. On the other hand, after the multi-walled carbon nano-tube is acidified and soaked in hydrofluoric acid, the product does not need to be cleaned and dried, but ammonia water and the hydrofluoric acid are firstly utilized for neutralization reaction to generate NH 4 F (ammonium fluoride) and remain in the system, wherein the function of the ammonium fluoride is that the ammonium fluoride can react with calcium-containing compounds in the cement to generate CaF in the final cement-based material 2 The protective layer can promote the improvement of the corrosion resistance and durability of cement and simplify the process.
In the invention, the content ratio of the tetracalcium aluminoferrite is improved by adding the tetracalcium aluminoferrite, so that the sulfate corrosion resistance of the cement can be improved, and the hydration product of the tetracalcium aluminoferrite is a solid solution of hydrated calcium aluminate and hydrated calcium ferrite, and is higher than C 3 AH 6 Has stronger sulfate erosion resistance.
The present invention is further illustrated by the following examples and comparative examples, which are given above for the purpose of illustrating the general inventive concept.
Example 1
The corrosion-resistant marine engineering cement comprises the following components in percentage by weight:
in this example, the cement clinker is a conventional portland cement clinker sold in the market, and the main components are: siO2 2 22.4％，Al 2 O 3 6.1％，Fe 2 O 3 4.2%, mgO 1.9%, the balance being CaO and small amounts of other impurities.
In the embodiment, the high-aluminum coal gangue comes from a certain coal mine in Shandong, and the high-aluminum coal gangue comprises the following main components in percentage by mass: al (Al) 2 O 3 32％、Fe 2 O 3 5.1 percent of MgO 3.3 percent of CaO 0.9 percent of the balance of SiO 2 Small amounts of other impurities. In this example, the multi-walled carbon nanotubes were purchased from institute of academic organic chemistry, ltd.
The coal gangue powder loading the carbon nanotubes is obtained by loading the multiwalled carbon nanotubes on porous high-aluminum coal gangue powder, and the specific preparation method comprises the following steps:
1) Preparing porous activated high-aluminum coal gangue powder by using high-aluminum coal gangue:
1-1) preparing porous high-aluminum coal gangue powder:
1-1-1) grinding the high-alumina coal gangue to a content of less than 200 meshes which is more than 95 percent to obtain coal gangue powder;
1-1-2) mixing the coal gangue powder with a foaming agent, uniformly stirring, adding water, and reacting for 4 hours under continuous stirring;
1-1-3) drying the product obtained in the step 1-1-2) under stirring, roasting at 900 ℃ for 6 hours, and crushing the product to obtain porous high-aluminum coal gangue powder;
1-2) carrying out activation modification on the high-alumina coal gangue powder to prepare porous high-alumina coal gangue powder:
dispersing the porous high-aluminum coal gangue powder obtained in the step 1-1) into ethanol, adding a coupling agent KH550 (gamma-aminopropyltriethoxysilane), ultrasonically dispersing for 0.5h, reacting for 4 hours at 95 ℃ under continuous stirring, centrifuging, cleaning a solid product, then adding the solid product into water, and stirring into a slurry state to obtain a slurry of the porous activated high-aluminum coal gangue powder for later use.
2) Preparing a modified multi-walled carbon nanotube solution:
the step 2) specifically comprises the following steps: adding the multi-walled carbon nano-tube into mixed acid of concentrated sulfuric acid (mass fraction 98%) and concentrated nitric acid (mass fraction 75%), ultrasonically dispersing for 30min, reacting for 2h at 80 ℃, separating out a solid product and washing;
and adding the solid product into hydrofluoric acid (mass fraction is 20%), soaking for 12 hours, adding ammonia water into the mixed solution, stirring for reaction until the pH value of the solution is 7, and stopping the reaction to obtain a modified multi-walled carbon nanotube solution for later use.
3) Preparing the coal gangue powder loaded with the carbon nano tubes by using porous activated high-aluminum coal gangue powder and a modified multi-walled carbon nano tube solution:
adding the modified multi-walled carbon nanotube solution obtained in the step 2) into the slurry of the porous activated high-aluminum coal gangue powder obtained in the step 1) under stirring, reacting for 6 hours under continuous stirring, drying in vacuum, and crushing the product to obtain the coal gangue powder loaded with the carbon nanotubes. In the coal gangue powder loading the carbon nano-tubes, the mass content of the multi-wall carbon nano-tubes is 1.2%.
The preparation method of the corrosion-resistant marine engineering cement comprises the following steps:
s1, mixing tetracalcium aluminoferrite, fly ash, silica fume, limestone powder and coal gangue powder loaded with carbon nanotubes according to a weight ratio, and grinding;
s2, uniformly mixing the mixed powder obtained in the step 1) with silicate cement clinker to obtain the corrosion-resistant marine engineering cement.
Example 2
The corrosion-resistant marine engineering cement comprises the following components in percentage by weight:
in this example, the cement clinker is a conventional portland cement clinker sold in the market, and the main components are: siO2 2 22.4％，Al 2 O 3 6.1％，Fe 2 O 3 4.2%, mgO 1.9%, the balance being CaO and small amounts of other impurities.
In the embodiment, the high-aluminum coal gangue comes from a certain coal mine in Shandong, and the high-aluminum coal gangue comprises the following main components in percentage by mass: 32% of Al2O3, 5.1% of Fe2O3, 3.3% of MgO, 0.9% of CaO and the balance of SiO2 and a small amount of other impurities. In this example, the multi-walled carbon nanotubes were purchased from national institute of organic chemistry, ltd.
The coal gangue powder loading the carbon nanotubes is obtained by loading the multiwalled carbon nanotubes on porous high-aluminum coal gangue powder, and the specific preparation method comprises the following steps:
1) Preparing porous activated high-aluminum coal gangue powder by using high-aluminum coal gangue:
1-1) preparing porous high-aluminum coal gangue powder:
1-1-1) grinding the high-alumina coal gangue to a content of less than 200 meshes which is more than 95 percent to obtain coal gangue powder;
1-1-2) mixing the gangue powder with a foaming agent, uniformly stirring, adding water, and reacting for 4 hours under continuous stirring;
1-1-3) drying the product obtained in the step 1-1-2) under stirring, then roasting for 6 hours at 900 ℃, and crushing the product to obtain porous high-alumina coal gangue powder;
1-2) carrying out activation modification on the high-aluminum coal gangue powder to prepare porous high-aluminum coal gangue powder:
dispersing the porous high-aluminum coal gangue powder obtained in the step 1-1) into ethanol, adding a coupling agent KH550 (gamma-aminopropyltriethoxysilane), ultrasonically dispersing for 0.5h, reacting for 4 hours under continuous stirring at 95 ℃, centrifuging, cleaning a solid product, adding into water, and stirring into a slurry state to obtain a slurry of the porous activated high-aluminum coal gangue powder for later use.
2) Preparing a modified multi-walled carbon nanotube solution:
the step 2) specifically comprises the following steps: adding the multi-walled carbon nano-tube into mixed acid of concentrated sulfuric acid (mass fraction 98%) and concentrated nitric acid (mass fraction 75%), ultrasonically dispersing for 30min, reacting for 2h at 80 ℃, separating out a solid product and washing;
and (3) adding the solid product into hydrofluoric acid (mass fraction of 20%), soaking for 12 hours, adding ammonia water into the mixed solution, stirring for reaction until the pH value of the solution is 7, and stopping the reaction to obtain a modified multi-wall carbon nanotube solution for later use.
3) Preparing the coal gangue powder loaded with the carbon nano tubes by using porous activated high-aluminum coal gangue powder and a modified multi-walled carbon nano tube solution:
adding the modified multi-walled carbon nanotube solution obtained in the step 2) into the slurry of the porous activated high-aluminum coal gangue powder obtained in the step 1) under stirring, reacting for 6 hours under continuous stirring, drying in vacuum, and crushing the product to obtain the coal gangue powder loaded with the carbon nanotubes. In the coal gangue powder loading the carbon nano-tube, the mass content of the multi-wall carbon nano-tube is 1.2%.
The preparation method of the corrosion-resistant marine engineering cement comprises the following steps:
s1, mixing tetracalcium aluminoferrite, fly ash, silica fume, limestone powder and coal gangue powder loaded with carbon nanotubes according to a weight ratio, and grinding;
s2, uniformly mixing the mixed powder obtained in the step 1) with silicate cement clinker to obtain the corrosion-resistant marine engineering cement.
Example 3
The corrosion-resistant marine engineering cement comprises the following components in percentage by weight:
the rest is portland cement clinker.
In this example, the cement clinker is a conventional portland cement clinker sold in the market, and the main components are: siO2 2 22.4％，Al2O3 6.1％，Fe2O 3 4.2%, mgO 1.9%, the balance being CaO and small amounts of other impurities.
In the embodiment, the high-aluminum coal gangue comes from a certain coal mine in Shandong, and the high-aluminum coal gangue comprises the following main components in percentage by mass: al (Al) 2 O 3 32％、Fe 2 5.1% of O3, 3.3% of MgO, 0.9% of CaO and the balance of SiO 2 Small amounts of other impurities. In this example, the multi-walled carbon nanotubes were purchased from national institute of organic chemistry, ltd.
The coal gangue powder loading the carbon nanotubes is obtained by loading the multiwalled carbon nanotubes on porous high-aluminum coal gangue powder, and the specific preparation method comprises the following steps:
1) Preparing porous activated high-aluminum coal gangue powder by using high-aluminum coal gangue:
1-1) preparing porous high-aluminum coal gangue powder:
1-1-1) grinding the high-alumina coal gangue to a content of less than 200 meshes which is more than 95 percent to obtain coal gangue powder;
1-1-2) mixing the coal gangue powder with a foaming agent, uniformly stirring, adding water, and reacting for 4 hours under continuous stirring;
1-1-3) drying the product obtained in the step 1-1-2) under stirring, roasting at 900 ℃ for 6 hours, and crushing the product to obtain porous high-aluminum coal gangue powder;
1-2) carrying out activation modification on the high-aluminum coal gangue powder to prepare porous high-aluminum coal gangue powder:
dispersing the porous high-aluminum coal gangue powder obtained in the step 1-1) into ethanol, adding a coupling agent KH550 (gamma-aminopropyltriethoxysilane), ultrasonically dispersing for 0.5h, reacting for 4 hours under continuous stirring at 95 ℃, centrifuging, cleaning a solid product, adding into water, and stirring into a slurry state to obtain a slurry of the porous activated high-aluminum coal gangue powder for later use.
2) Preparing a modified multi-walled carbon nanotube solution:
the step 2) specifically comprises the following steps: adding the multi-walled carbon nano-tube into mixed acid of concentrated sulfuric acid (mass fraction of 98%) and concentrated nitric acid (mass fraction of 75%), performing ultrasonic dispersion for 30min, reacting for 2h at 80 ℃, separating out a solid product and washing;
and adding the solid product into hydrofluoric acid (mass fraction is 20%), soaking for 12 hours, adding ammonia water into the mixed solution, stirring for reaction until the pH value of the solution is 7, and stopping the reaction to obtain a modified multi-walled carbon nanotube solution for later use.
3) Preparing the coal gangue powder loaded with the carbon nano tubes by using porous activated high-aluminum coal gangue powder and a modified multi-walled carbon nano tube solution:
adding the modified multi-walled carbon nanotube solution obtained in the step 2) into the slurry of the porous activated high-aluminum coal gangue powder obtained in the step 1) under stirring, reacting for 6 hours under continuous stirring, drying in vacuum, and crushing the product to obtain the coal gangue powder loaded with the carbon nanotubes. In the coal gangue powder loading the carbon nano-tubes, the mass content of the multi-wall carbon nano-tubes is 1.5%.
The preparation method of the corrosion-resistant marine engineering cement comprises the following steps:
s1, mixing tetracalcium aluminoferrite, fly ash, silica fume, limestone powder and coal gangue powder loaded with carbon nanotubes according to a weight ratio, and grinding;
s2, uniformly mixing the mixed powder obtained in the step 1) with silicate cement clinker to obtain the corrosion-resistant marine engineering cement.
Comparative example 1
This example is substantially the same as example 1, except that: the cement in the embodiment comprises the following components in percentage by weight:
comparative example 2
This example is substantially the same as example 1, except that: the cement in the embodiment comprises the following components in percentage by weight:
the high-alumina coal gangue is ground to a content of more than 95% below 200 meshes to obtain the high-alumina coal gangue powder, wherein the high-alumina coal gangue is the same as that in the embodiment 1.
The following performance tests were performed on the cements prepared in examples 1-3 and comparative examples 1-5 as follows:
(1) Testing the anti-sulfate erosion coefficient by referring to a GB/T749-2008 standard K method;
(2) Determining the diffusion coefficient of chloride ions according to JC/T1086;
(3) Testing the strength according to GB/T17671-1999 standard for 3 days and 28 days;
from the results of examples 1-3, it can be seen that the corrosion-resistant marine cement prepared by the present invention has excellent sulfate and chloride ion corrosion resistance. It can be seen from the comparison between comparative examples 1 and 2 and example 1 that the coal gangue powder loaded with carbon nanotubes has a significant enhancing effect on the improvement of the anti-corrosion performance of cement, and when the multi-walled carbon nanotubes and the high-alumina coal gangue powder are added separately, the effect of improving the anti-corrosion performance of cement is limited because the defect that the multi-walled carbon nanotubes are easy to agglomerate cannot be overcome.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the details shown in the description and the examples, which are set forth, but are fully applicable to various fields of endeavor as are suited to the particular use contemplated, and further modifications will readily occur to those skilled in the art, since the invention is not limited to the details shown and described without departing from the general concept as defined by the appended claims and their equivalents.
Claims (10)
1. The corrosion-resistant marine cement is characterized by comprising the following components in percentage by weight:
the balance being cement clinker.
2. The corrosion resistant marine cement of claim 1, wherein said cement clinker is a portland cement clinker.
3. The corrosion-resistant marine cement according to claim 2, wherein the carbon nanotube-loaded coal gangue powder is obtained by loading multi-walled carbon nanotubes on porous high-alumina coal gangue powder, and the specific preparation method comprises the following steps:
1) Preparing porous activated high-alumina coal gangue powder by using high-alumina coal gangue;
2) Preparing a modified multi-walled carbon nanotube solution;
3) The coal gangue powder loaded with the carbon nano tubes is prepared by utilizing porous activated high-aluminum coal gangue powder and a modified multi-wall carbon nano tube solution.
4. The corrosion-resistant marine cement according to claim 3, wherein the step 1) specifically comprises:
1-1) preparing porous high-aluminum coal gangue powder:
1-1-1) grinding the high-alumina coal gangue to the content of less than 200 meshes which is more than 95 percent to obtain coal gangue powder;
1-1-2) mixing the coal gangue powder and the aluminum powder, uniformly stirring, adding water, and reacting under continuous stirring;
1-1-3) drying and roasting the product obtained in the step 1-1-2) under stirring, and crushing the product to obtain porous high-aluminum coal gangue powder;
1-2) carrying out activation modification on the high-alumina coal gangue powder to prepare porous high-alumina coal gangue powder:
dispersing the porous high-aluminum coal gangue powder obtained in the step 1-1) into ethanol, adding gamma-aminopropyl triethoxysilane, ultrasonically dispersing, reacting under the conditions of heating and continuous stirring, centrifuging after the reaction is finished, cleaning a solid product, then adding the solid product into water, and stirring the solid product into a slurry state to obtain slurry of the porous activated high-aluminum coal gangue powder for later use.
5. The corrosion-resistant marine cement according to claim 4, wherein the step 1) specifically comprises:
1-1) preparing porous high-aluminum coal gangue powder:
1-1-1) grinding the high-alumina coal gangue to the content of less than 200 meshes which is more than 95 percent to obtain coal gangue powder;
1-1-2) mixing the coal gangue powder with a foaming agent, uniformly stirring, adding water, and reacting for 3-8h under continuous stirring;
1-1-3) drying the product obtained in the step 1-1-2) under stirring, then roasting for 4-10h at 700-950 ℃, and crushing the product to obtain porous high-aluminum coal gangue powder;
1-2) carrying out activation modification on the high-aluminum coal gangue powder to prepare porous high-aluminum coal gangue powder:
dispersing the porous high-aluminum coal gangue powder obtained in the step 1-1) into ethanol, adding gamma-aminopropyl triethoxysilane, ultrasonically dispersing for 0.5-2h, reacting for 3-8h at 80-115 ℃ under continuous stirring, centrifuging, cleaning a solid product, adding into water, and stirring into a slurry state to obtain a slurry of the porous activated high-aluminum coal gangue powder for later use.
6. A corrosion resistant marine cement according to claim 5, wherein said step 2) specifically comprises: adding a multi-walled carbon nano tube into mixed acid of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic dispersion, reacting under a heating condition, and after the reaction is finished, separating out a solid product and washing;
and (3) adding the solid product into hydrofluoric acid, soaking, adding ammonia water into the mixed solution, stirring for reaction until the pH value of the solution is 6.5-7, and stopping the reaction to obtain a modified multi-wall carbon nanotube solution for later use.
7. A corrosion resistant marine cement according to claim 6, wherein said step 2) comprises in particular: adding the multi-walled carbon nano-tube into mixed acid of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic dispersion for 15-60min, reacting for 0.5-3h at 75-100 ℃, separating out a solid product and washing;
and adding the solid product into hydrofluoric acid, soaking for 6-24 hours, adding ammonia water into the mixed solution, stirring for reaction until the pH value of the solution is 6.5-7, and stopping the reaction to obtain a modified multi-walled carbon nanotube solution for later use.
8. A corrosion resistant marine cement according to claim 7, wherein said step 3) comprises in particular: adding the modified multi-walled carbon nanotube solution obtained in the step 2) into the slurry of the porous activated high-aluminum coal gangue powder obtained in the step 1) under stirring, reacting for 2-10h under continuous stirring, drying in vacuum, and crushing the product to obtain the coal gangue powder loaded with the carbon nanotubes.
9. The corrosion resistant marine cement of claim 8, wherein said high alumina gangue powder comprises Al 2 O 3 The mass percentage content is more than 28 percent.
10. A method of preparing a corrosion resistant marine cement according to any one of claims 1 to 9, comprising the steps of:
s1, mixing tetracalcium aluminoferrite, fly ash, silica fume, limestone powder and coal gangue powder loaded with carbon nanotubes according to a weight ratio, and grinding;
s2, uniformly mixing the mixed powder obtained in the step 1) with silicate cement clinker to obtain the corrosion-resistant marine engineering cement.
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|---|---|---|---|---|
| CN115947579A (en) * | 2022-12-27 | 2023-04-11 | 哈尔滨工业大学 | Preparation method of underwater micro-nano cementing material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225516A (en) * | 2020-10-12 | 2021-01-15 | 桂林理工大学 | High-speed rail marine Portland cement and preparation method and application thereof |
| CN112321204A (en) * | 2020-10-10 | 2021-02-05 | 上海友品环境服务有限公司 | Formula and process for compounding and comprehensive resource utilization of coal gangue and coal ash |
| CN112679117A (en) * | 2021-01-28 | 2021-04-20 | 青岛大明新型建材有限公司 | High-performance portland cement and preparation method thereof |
-
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- 2022-08-03 CN CN202210924957.XA patent/CN115196893B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321204A (en) * | 2020-10-10 | 2021-02-05 | 上海友品环境服务有限公司 | Formula and process for compounding and comprehensive resource utilization of coal gangue and coal ash |
| CN112225516A (en) * | 2020-10-12 | 2021-01-15 | 桂林理工大学 | High-speed rail marine Portland cement and preparation method and application thereof |
| CN112679117A (en) * | 2021-01-28 | 2021-04-20 | 青岛大明新型建材有限公司 | High-performance portland cement and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘在春: "《铁铝酸盐水泥在海工混凝土中的应用》", 《中华建设》 * |
| 高金瑞等: "《铁相组分对铁相和高铁低钙水泥熟料水化性能及抗侵蚀性能影响》", 《硅酸盐通报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115947579A (en) * | 2022-12-27 | 2023-04-11 | 哈尔滨工业大学 | Preparation method of underwater micro-nano cementing material |
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