CN111925138B - Environment-friendly building cement and preparation method thereof - Google Patents

Environment-friendly building cement and preparation method thereof Download PDF

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CN111925138B
CN111925138B CN202010822670.7A CN202010822670A CN111925138B CN 111925138 B CN111925138 B CN 111925138B CN 202010822670 A CN202010822670 A CN 202010822670A CN 111925138 B CN111925138 B CN 111925138B
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environment
cement
friendly building
dried sludge
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CN111925138A (en
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张勇
刘洪涛
吴学华
张嘉欣
邢康哲
康亚男
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Zhang Yong
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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
    • 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
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/48—Clinker treatment
    • C04B7/52—Grinding ; After-treatment of ground cement
    • 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)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses environment-friendly building cement which is characterized by comprising the following raw materials in parts by weight: 40-60 parts of cement clinker, 5-10 parts of modified dried sludge, 6-12 parts of desulfurized ash, 3-5 parts of waste polyester fiber, 10-15 parts of calcite powder, 1-2 parts of rare earth metal organic framework and 1-5 parts of N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester). The invention also discloses a preparation method of the environment-friendly building cement. The environment-friendly building cement disclosed by the invention has the advantages of good comprehensive performance, long service life, good use effect, good strength, grinding aid effect, hydration efficiency, workability and water retention performance, is not easy to crack, hollowing and the like, and has excellent environment-friendly performance.

Description

Environment-friendly building cement and preparation method thereof
Technical Field
The invention relates to the technical field of building materials, in particular to environment-friendly building cement and a preparation method thereof.
Background
In recent years, with the rapid development of national economy, the pace of infrastructure construction has been advancing. The demand for various building materials has increased year by year. The cement serves as the largest branch of building materials, plays an important role in human social infrastructure construction activities such as building high-rise buildings, paving roads, erecting bridges, building subways and the like, and greatly improves human living, working and traveling environments. It can be seen that the development of cement with excellent properties is of great importance to improve the quality of construction projects.
The cement is a powdery hydraulic inorganic cementing material. The water is added and stirred to form slurry which can be hardened in the air or better hardened in the water and can firmly bond sand, stone and other materials together. It is one of three basic materials in the building industry, has large usage amount and wide application range, and is called as 'grains in the building industry'. Because of its relatively excellent performance and low production cost. The method is widely applied to the engineering fields of civil construction, water conservancy, national defense and the like. However, the use of cement brings great convenience to human beings, and simultaneously brings great negative effects to the ecological environment of people. Because of the traditional cement or the special cement, the coal and the raw materials are very serious in the manufacturing process, the production process is complex, and not only is the resource waste caused, but also the environmental pollution is caused. In addition, cement in the prior art generally has the phenomena of short service life, poor effect, insufficient strength, insufficient water retention rate, easy cracking, hollowing and the like, and the grinding aiding effect, the hydration efficiency and the workability are all to be further improved.
The Chinese patent with application number 201610722399.3 discloses a cement formula, which comprises the following raw materials in parts by weight: 20-40 parts of cement clinker, 10-20 parts of limestone, 10-30 parts of carbide slag, 5-10 parts of slag, 10-20 parts of anhydrous gypsum, 1-10 parts of pigment, 10-20 parts of fluorgypsum, 10-30 parts of ash, 10-30 parts of sandstone and 12-15 parts of manganese slag. The invention provides the cement manufactured by using industrial waste materials, the formula is scientific and reasonable, the cement manufacturing cost is effectively reduced, and meanwhile, the ecological environment is improved by using the waste materials to manufacture the cement, thereby conforming to the environmental protection concept. However, the cement has poor comprehensive performance due to no addition of additives, and particularly, the strength, the grinding aid effect, the hydration efficiency, the workability and the service life of the cement are to be further improved.
Therefore, the environment-friendly building cement with long service life, good use effect, good strength, grinding-aid effect, hydration efficiency, good workability and good water-retaining property is developed, the phenomena of cracking, hollowing and the like are not easy to occur, the environment-friendly building cement with excellent environment-friendly property meets the market demand, has wide market value and application prospect, and plays an important role in promoting the development of the cement field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the environment-friendly building cement which has the advantages of good comprehensive performance, long service life, good use effect, good strength, grinding aid effect, hydration efficiency, workability and water retention performance, is not easy to crack, hollows and the like, and has excellent environment-friendly performance. Meanwhile, the invention also provides a preparation method of the environment-friendly building cement, which is simple and feasible, has easily obtained preparation raw materials, high preparation efficiency and convenient construction, and is suitable for continuous large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that: the environment-friendly building cement is characterized by comprising the following raw materials in parts by weight: 40-60 parts of cement clinker, 5-10 parts of modified dried sludge, 6-12 parts of desulfurized ash, 3-5 parts of waste polyester fiber, 10-15 parts of calcite powder, 1-2 parts of rare earth metal organic framework and 1-5 parts of N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester).
Preferably, the cement clinker is ordinary portland cement clinker.
Preferably, the preparation method of the modified dried sludge comprises the following steps: dispersing the dried sludge in an organic solvent, adding N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine, stirring and reacting at 50-70 ℃ for 3-5 hours, and then removing the solvent by rotary evaporation to obtain the modified dried sludge.
Preferably, the mass ratio of the dried sludge, the organic solvent and the N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine is 1 (3-5) to 0.1-0.2.
Preferably, the organic solvent is any one of ethanol, dichloromethane and acetone.
Preferably, the dried sludge is paper-making waste paper sludge, and the performance indexes of the dried sludge are as follows: the content of effective calcium and magnesium is more than 30 percent, the content of particles with the diameter less than 5mm is more than 70 percent, and the water content is 10 to 25 percent.
Preferably, the waste polyester fibers are subjected to shearing treatment before use, and are sourced from waste polyester textile fabrics.
Preferably, the preparation method of the rare earth metal organic framework is the prior art, which is referred to as Chinese patent application No. 201710666255.5, example 1.
Preferably, the preparation method of the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy-terminated hyperbranched poly (amine-ester) comprises the following steps: adding epoxy-terminated hyperbranched poly (amine-ester) into a high-boiling-point solvent, adding N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid into the solvent, stirring the mixture at 70-80 ℃ for reaction for 4-6 hours, precipitating the mixture in water, and drying the precipitated polymer in a vacuum drying oven at 85-95 ℃ to constant weight to obtain the N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy-terminated hyperbranched poly (amine-ester).
Preferably, the mass ratio of the epoxy terminal hyperbranched poly (amine-ester), the high-boiling point solvent and the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid is 1 (3-5) to (0.2-0.3).
Preferably, the preparation method of the epoxy-terminated hyperbranched poly (amine-ester) is the prior art, which is referred to as chinese patent application No. 200910067539.8, example 6.
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
The invention also aims to provide a preparation method of the environment-friendly building cement, which is characterized by comprising the following steps: mixing the raw materials according to the parts by weight, and grinding together until the specific surface area is 150-2And/kg, obtaining the environment-friendly building cement.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the preparation method of the environment-friendly building cement provided by the invention has the advantages that the raw materials are mixed and ground to obtain the environment-friendly building cement, special equipment is not required, the preparation process is simple, the operation and the control are convenient, the raw materials are easy to obtain, the preparation efficiency is high, toxic and harmful substances are not generated in the preparation process, the labor intensity is low, the environment-friendly building cement is suitable for industrial production, and the environment-friendly building cement has higher economic value, social value and ecological value.
(2) The environment-friendly building cement overcomes the defects that cement in the prior art generally has short service life, poor effect, insufficient strength, insufficient water retention rate, easy cracking, hollowing and the like, and the grinding aiding effect, the hydration efficiency and the workability are all required to be further improved.
(3) The environment-friendly building cement provided by the invention is a composition formed by reasonably matching various raw materials, and the prior art does not disclose that the raw materials are combined and added into the composition to prepare the cement, nor does the prior art suggest the corresponding technology. The prepared cement has excellent comprehensive performance, and the doping of industrial wastes such as modified dried sludge, desulfurized ash and waste polyester fiber not only improves the comprehensive performance of the cement, but also realizes the recycling of waste resources, avoids the waste of resources, is also beneficial to environmental protection and effectively realizes the improvement of ecological efficiency; the addition amount of cement clinker is reduced, and the cost is reduced to a certain extent.
(4) According to the environment-friendly building cement provided by the invention, the added modified dried sludge is subjected to surface modification, so that the compatibility of the modified dried sludge with other components is enhanced, the modified dried sludge and other raw materials play a role in enhancing, and the introduction of surface active hydroxyl can effectively improve the water retention performance and reduce the risks of bubbling and dry cracking; the fiber structure of the waste polyester fiber can be well reinforced, ester hydrolysis can occur in a cement alkaline system to form carboxyl, the concrete structure is prevented from being stable, collapse is prevented, PH is adjusted, and the alkali inhibitor, the water reducer and the grinding aid are used. The calcite powder and other components have synergistic effect, so that the hydration reaction can be accelerated, and the early strength is improved.
(5) According to the environment-friendly building cement provided by the invention, due to the cavity structure, other raw materials can be embedded in the cavity structure, so that the strength of the cement is increased, the cracking of the cement is prevented, the hydration process of the cement can be promoted by adding the rare earth metal, and the hydration microstructure of the cement concrete is compacted, so that the early strength of the cement is improved, the performance stability of the cement can also be improved, and the effects of improving the quality of the cement and prolonging the service life of the cement are achieved. The added N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester) is modified by N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid, under the action of large steric hindrance and electronic effect of hyperbranched molecules, the effects of early strength, pumping, retarding, water reducing and air entraining are achieved, the occurrence of the phenomenon of saltpetering is avoided, the functions are obtained by adding one component, the antagonism caused by adding various components is effectively avoided, the comprehensive performance and the performance stability of cement are favorably improved, and the tertiary amino structure contained on the hyperbranched poly (amine-ester) can play a role in complexation and improve the early strength. And the introduction of the multi-active group of the substance enables the cement paste to be more compact in the processes of stirring, setting and hardening, improves the grinding aiding performance, improves the powder grinding effect of the cement, and further can improve the comprehensive performance of the cement.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made. The preparation method of the epoxy terminal hyperbranched poly (amine-ester) is the prior art, and is shown in Chinese invention patent example 6 with the application number of 200910067539.8; the waste polyester fibers are subjected to shearing treatment before use, and are sourced from waste polyester textile fabrics; the preparation method of the rare earth metal organic framework is the prior art, and is shown in the patent example 1 of Chinese invention with the application number of 201710666255.5; the cement clinker is common Portland cement clinker; the dried sludge is paper making waste paper sludge, and the performance indexes of the dried sludge are as follows: the content of effective calcium and magnesium is more than 30 percent, the content of particles with the diameter less than 5mm is more than 70 percent, and the water content is 10 to 25 percent.
The invention will be further described with reference to specific examples, but the scope of protection of the invention is not limited thereto:
example 1
The embodiment 1 provides environment-friendly building cement which is characterized by comprising the following raw materials in parts by weight: 40 parts of cement clinker, 5 parts of modified dried sludge, 6 parts of desulfurized ash, 3 parts of waste polyester fiber, 10 parts of calcite powder, 1 part of rare earth metal organic framework and 1 part of N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester).
The preparation method of the modified dried sludge comprises the following steps: dispersing the dried sludge in an organic solvent, adding N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine into the dried sludge, stirring the mixture at the temperature of 50 ℃ for reaction for 3 hours, and then performing rotary evaporation to remove the solvent to obtain modified dried sludge; the mass ratio of the dried sludge to the organic solvent to the N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine is 1:3: 0.1; the organic solvent is ethanol.
The preparation method of the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy-terminated hyperbranched poly (amine-ester) comprises the following steps: adding epoxy end group hyperbranched poly (amine-ester) into a high boiling point solvent, adding N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid into the solvent, stirring the mixture at 70 ℃ for reaction for 4 hours, precipitating the mixture in water, and drying the precipitated polymer in a vacuum drying oven at 85 ℃ to constant weight to obtain N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester); the mass ratio of the epoxy terminal hyperbranched poly (amine-ester), the high-boiling point solvent and the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid is 1:3: 0.2; the high boiling point solvent is dimethyl sulfoxide.
The preparation method of the environment-friendly building cement is characterized by comprising the following steps of: mixing the raw materials according to the weight part, and grinding together until the specific surface area is 150m2And/kg, obtaining the environment-friendly building cement.
Example 2
Embodiment 2 provides an environmental protection building cement, which is characterized by comprising the following raw materials in parts by weight: 45 parts of cement clinker, 6 parts of modified dried sludge, 7 parts of desulfurized ash, 3.5 parts of waste polyester fiber, 11 parts of calcite powder, 1.2 parts of rare earth metal organic framework and 2 parts of N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester).
The preparation method of the modified dried sludge comprises the following steps: dispersing the dried sludge in an organic solvent, adding N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine into the dried sludge, stirring the mixture at the temperature of 55 ℃ for reaction for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain modified dried sludge; the mass ratio of the dried sludge to the organic solvent to the N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine is 1:3.5: 0.12; the organic solvent is dichloromethane.
The preparation method of the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy-terminated hyperbranched poly (amine-ester) comprises the following steps: adding epoxy end group hyperbranched poly (amine-ester) into a high boiling point solvent, adding N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid into the solvent, stirring the mixture at 73 ℃ for reaction for 4.5 hours, precipitating the mixture in water, and drying the precipitated polymer in a vacuum drying oven at 87 ℃ to constant weight to obtain N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester); the mass ratio of the epoxy terminal hyperbranched poly (amine-ester), the high-boiling point solvent and the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid is 1:3.5: 0.23; the high boiling point solvent is N, N-dimethylformamide.
The preparation method of the environment-friendly building cement is characterized by comprising the following steps of: mixing the raw materials according to the weight part, and grinding together until the specific surface area is 170m2And/kg, obtaining the environment-friendly building cement.
Example 3
Embodiment 3 provides an environment-friendly building cement, which is characterized by comprising the following raw materials in parts by weight: 50 parts of cement clinker, 7 parts of modified dried sludge, 8 parts of desulfurized ash, 4 parts of waste polyester fiber, 13 parts of calcite powder, 1.5 parts of rare earth metal organic framework and 3.5 parts of N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester).
The preparation method of the modified dried sludge comprises the following steps: dispersing the dried sludge in an organic solvent, adding N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine, stirring and reacting for 4 hours at 60 ℃, and then performing rotary evaporation to remove the solvent to obtain modified dried sludge; the mass ratio of the dried sludge to the organic solvent to the N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine is 1:4: 0.15; the organic solvent is acetone.
The preparation method of the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy-terminated hyperbranched poly (amine-ester) comprises the following steps: adding epoxy end group hyperbranched poly (amine-ester) into a high boiling point solvent, adding N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid into the solvent, stirring the mixture at the temperature of 75 ℃ for reaction for 5 hours, precipitating the mixture in water, and drying the precipitated polymer in a vacuum drying oven at the temperature of 90 ℃ to constant weight to obtain N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester); the mass ratio of the epoxy terminal hyperbranched poly (amine-ester), the high-boiling point solvent and the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid is 1:4: 0.25; the high boiling point solvent is N, N-dimethylacetamide.
The preparation method of the environment-friendly building cement is characterized by comprising the following steps of: mixing the raw materials according to the weight part, and grinding together until the specific surface area is 200m2And/kg, obtaining the environment-friendly building cement.
Example 4
Embodiment 4 provides an environment-friendly building cement, which is characterized by comprising the following raw materials in parts by weight: 55 parts of cement clinker, 9 parts of modified dried sludge, 11 parts of desulfurized ash, 4.5 parts of waste polyester fiber, 14 parts of calcite powder, 1.8 parts of rare earth metal organic framework and 4.5 parts of N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester).
The preparation method of the modified dried sludge comprises the following steps: dispersing the dried sludge in an organic solvent, adding N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine into the dried sludge, stirring the mixture at 68 ℃ for reacting for 4.5 hours, and then performing rotary evaporation to remove the solvent to obtain modified dried sludge; the mass ratio of the dried sludge to the organic solvent to the N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine is 1:4.5: 0.18; the organic solvent is ethanol.
The preparation method of the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy-terminated hyperbranched poly (amine-ester) comprises the following steps: adding epoxy end group hyperbranched poly (amine-ester) into a high boiling point solvent, adding N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid into the solvent, stirring the mixture at 78 ℃ for reaction for 5.5 hours, precipitating the mixture in water, and drying the precipitated polymer in a vacuum drying oven at 93 ℃ to constant weight to obtain N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester); the mass ratio of the epoxy terminal hyperbranched poly (amine-ester), the high-boiling point solvent and the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid is 1:4.5: 0.28; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:3: 2.
The preparation method of the environment-friendly building cement is characterized by comprising the following steps of: mixing the raw materials according to the weight part, and grinding together until the specific surface area is 240m2And/kg, obtaining the environment-friendly building cement.
Example 5
Embodiment 5 provides an environmental protection building cement, which is characterized by comprising the following raw materials in parts by weight: 60 parts of cement clinker, 10 parts of modified dried sludge, 12 parts of desulfurized ash, 5 parts of waste polyester fiber, 15 parts of calcite powder, 2 parts of rare earth metal organic framework and 5 parts of N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester).
The preparation method of the modified dried sludge comprises the following steps: dispersing the dried sludge in an organic solvent, adding N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine, stirring and reacting for 5 hours at 70 ℃, and then performing rotary evaporation to remove the solvent to obtain modified dried sludge; the mass ratio of the dried sludge to the organic solvent to the N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine is 1:5: 0.2; the organic solvent is dichloromethane.
The preparation method of the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy-terminated hyperbranched poly (amine-ester) comprises the following steps: adding epoxy end group hyperbranched poly (amine-ester) into a high boiling point solvent, adding N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid into the solvent, stirring the mixture at the temperature of 80 ℃ for reaction for 6 hours, precipitating the mixture in water, and drying the precipitated polymer in a vacuum drying oven at the temperature of 95 ℃ to constant weight to obtain N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester); the mass ratio of the epoxy terminal hyperbranched poly (amine-ester), the high-boiling point solvent and the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid is 1:5: 0.3; the high boiling point solvent is N-methyl pyrrolidone.
The preparation method of the environment-friendly building cement is characterized by comprising the following steps of: weighing the raw materialsMixing the components in parts by weight, and grinding the components together until the specific surface area is 250m2And/kg, obtaining the environment-friendly building cement.
Comparative example 1
Comparative example 1 provides an environmentally friendly construction cement having a formulation and a preparation method substantially the same as those of example 1 except that no modified dried sludge is added.
Comparative example 2
Comparative example 2 provides an environmentally friendly construction cement having a formulation and a preparation method substantially the same as those of example 1, except that the modified dried sludge is replaced with dried sludge.
Comparative example 3
Comparative example 3 provides an environmentally friendly construction cement having a formulation and a preparation method substantially the same as those of example 1, except that no waste polyester fiber is added.
Comparative example 4
Comparative example 4 provides an eco-friendly construction cement whose formulation and preparation method are substantially the same as those of example 1, except that no rare earth metal organic framework is added.
Comparative example 5
Comparative example 5 provides an environmentally friendly construction cement having a formulation and method of preparation substantially the same as example 1 except that no N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy-terminated hyperbranched poly (amine-ester) is added.
Comparative example 6
Comparative example 6 provides an environmentally friendly construction cement having substantially the same formulation and preparation method as in example 1, except that an epoxy-terminated hyperbranched poly (amine-ester) is used in place of the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid-modified epoxy-terminated hyperbranched poly (amine-ester).
The cements obtained in the above examples 1 to 5 and comparative examples 1 to 6 were subjected to the performance test, the test results are shown in Table 1, and the test methods are as follows:
(1) compressive strength: reference is made to the national standard GB/T17671.
(2) Water resistance and stability: 2kg of cement is taken, 0.5kg of water is added, and the mixture is uniformly stirred in a stirrer to prepare cement paste. The slurry was placed in a mold having a size of 30X 120mm to prepare a cement block. Standing and curing for 10 days at 22 ℃, and after curing, evaluating the water resistance and stability of the product by using the cement test block manufactured by the mold; soaking the prepared cement test block in water for 24 hours, then placing the cement test block in a drying environment at 30 ℃ for 24 hours for 5 cycles, and calculating the dissolution rate; the prepared cement test block is placed outdoors for six months, and the surface is observed whether obvious damage and change exist.
(3) Corrosion resistance coefficient: the method is carried out by referring to the national standard GB-T749-2008.
(4) Degree of hydration: the method is carried out by reference to the national standard GB/T12959-2008.
TABLE 1
Figure DEST_PATH_IMAGE001
As can be seen from Table 1, the environment-friendly building cement disclosed in the examples of the present invention has more excellent corrosion resistance and water resistance, higher compressive strength, higher hydration efficiency and more excellent performance stability, which are the result of the synergistic effect of the raw materials, compared with the comparative examples.
The above-mentioned embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (6)

1. The environment-friendly building cement is characterized by comprising the following raw materials in parts by weight: 40-60 parts of cement clinker, 5-10 parts of modified dried sludge, 6-12 parts of desulfurized ash, 3-5 parts of waste polyester fiber, 10-15 parts of calcite powder, 1-2 parts of rare earth metal organic framework and 1-5 parts of N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester);
the preparation method of the modified dried sludge comprises the following steps: dispersing the dried sludge in an organic solvent, adding N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine, stirring and reacting at 50-70 ℃ for 3-5 hours, and then removing the solvent by rotary evaporation to obtain modified dried sludge; the mass ratio of the dried sludge to the organic solvent to the N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine is 1 (3-5) to 0.1-0.2;
the preparation method of the N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy-terminated hyperbranched poly (amine-ester) comprises the following steps: adding epoxy end group hyperbranched poly (amine-ester) into a high boiling point solvent, adding N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid into the solvent, stirring the mixture at 70-80 ℃ for reaction for 4-6 hours, precipitating the mixture in water, and drying the precipitated polymer in a vacuum drying oven at 85-95 ℃ to constant weight to obtain N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid modified epoxy end group hyperbranched poly (amine-ester); the mass ratio of the epoxy end group hyperbranched poly (amine-ester), the high boiling point solvent and the N-tri (hydroxymethyl) methyl-2-aminoethanesulfonic acid is 1 (3-5) to 0.2-0.3; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
2. The environment-friendly building cement as claimed in claim 1, wherein the cement clinker is ordinary portland cement clinker.
3. The environment-friendly building cement as claimed in claim 1, wherein the organic solvent is any one of ethanol, dichloromethane and acetone.
4. The environment-friendly building cement as claimed in claim 1, wherein the dried sludge is paper-making waste paper sludge, and the performance indexes of the dried sludge are as follows: the content of effective calcium and magnesium is more than 30 percent, the content of particles with the diameter less than 5mm is more than 70 percent, and the water content is 10 to 25 percent.
5. The environment-friendly building cement as claimed in claim 1, wherein the waste polyester fiber is subjected to shearing treatment before use to obtain waste polyester textile fabric.
6. The environment-friendly building cement as claimed in any one of claims 1 to 5, wherein the preparation method of the environment-friendly building cement comprises the following steps: mixing the raw materials according to the parts by weight, and grinding together until the specific surface area is 150-2And/kg, obtaining the environment-friendly building cement.
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