CN113620623B - Magnesium silicate gel material and preparation method and application thereof - Google Patents

Magnesium silicate gel material and preparation method and application thereof Download PDF

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Publication number
CN113620623B
CN113620623B CN202111107313.3A CN202111107313A CN113620623B CN 113620623 B CN113620623 B CN 113620623B CN 202111107313 A CN202111107313 A CN 202111107313A CN 113620623 B CN113620623 B CN 113620623B
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powder
magnesium silicate
auxiliary material
mass ratio
serpentine
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CN113620623A (en
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彭同江
罗利明
孙红娟
唐颂
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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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
    • C04B9/00—Magnesium cements or similar cements
    • C04B9/11—Mixtures thereof with other inorganic cementitious materials
    • C04B9/12—Mixtures thereof with other inorganic cementitious materials with hydraulic cements, e.g. Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B9/00—Magnesium cements or similar cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B9/00—Magnesium cements or similar cements
    • C04B9/20—Manufacture, e.g. preparing the batches
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

The invention provides a magnesium silicate cementing material, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing a raw material containing serpentine minerals and a first auxiliary material according to a first preset mass ratio, and pretreating to obtain a first powder, wherein the first auxiliary material is at least one of carbonate minerals and carbonate mineral tailings; the first predetermined mass ratio includes a case where the first amount of the auxiliary material is 0; calcining the first powder to obtain a second powder with the main crystal phase of olivine; mixing second powder particles and a second auxiliary material according to a second preset mass ratio, and grinding to obtain a magnesium silicate cementing material, wherein the second auxiliary material is at least one of lime, carbonate cement clinker, carbide slag, gypsum and water glass powder; the second predetermined mass ratio includes a case where the second amount of the auxiliary material is 0. The magnesium silicate cementing material powder has the gelling property after being mixed with water, and a formed body is cured into a stone body, so that the stone body has high strength, good stability, no expansion after water absorption, no frost return and strong durability.

Description

Magnesium silicate gel material and preparation method and application thereof
Technical Field
The invention relates to the technical field of gelled materials of building material processes, in particular to a magnesium silicate gelled material, a preparation method of the magnesium silicate gelled material and application of the magnesium silicate gelled material.
Background
The magnesium silicate gel material is a magnesium-based gel material taking magnesium silicate as a main component, and plays an important role in the building industry. Such as portland cement cementitious materials in general, are widely used in civil buildings and general industrial buildings. The implementation of the national novel urbanization plan can continuously promote the application of green building materials, and the utilization of solid waste resources is the key direction for developing the green environment-friendly building material industry.
The magnesium silicate gel can be prepared by compounding silica fume with magnesium oxide, or by using soluble SiO 2 Formed by reaction with magnesium oxide. Or by calcining minerals containing oxides of silicon and magnesium, e.g. by calcining magnesite tailings to obtain magnesium oxide, and then calcining the magnesium oxideOne step with active SiO 2 And preparing the magnesium silicate gel system cement by using a series of additives. The above methods all have problems that magnesium oxide or SiO with high purity and good activity is required in the production process of magnesium silicate gel powder 2 As raw materials, the raw materials have high market price, and the production of the raw materials also needs a large amount of energy consumption, thus being not in accordance with the concept of green environmental protection.
Disclosure of Invention
The present invention aims to address at least one of the above-mentioned deficiencies of the prior art. For example, one of the purposes of the invention is to provide a preparation method for producing a magnesium silicate cementing material by using rocks, waste rocks and tailings mainly containing serpentine as raw materials and using a resource utilization technology.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a magnesium silicate cement, comprising the steps of:
mixing a raw material containing serpentine minerals and a first auxiliary material according to a first preset mass ratio, and pretreating to obtain a first powder, wherein the first auxiliary material is at least one of carbonate minerals and carbonate mineral tailings; the first predetermined mass ratio includes a case where the first amount of the auxiliary material is 0;
calcining the first powder to obtain a second powder with the main crystal phase of olivine;
mixing second powder particles and a second auxiliary material according to a second preset mass ratio, and grinding to obtain a magnesium silicate cementing material, wherein the second auxiliary material is at least one of lime, carbonate cement clinker, carbide slag, gypsum and water glass powder; the second predetermined mass ratio includes a case where the second amount of the auxiliary material is 0.
In one exemplary embodiment of the method for preparing a magnesium silicate cementitious material of the present invention, the serpentine mineral-containing raw material may include at least one of serpentine, serpentine mill tailings, chrysotile mill tailings, ultrabedrock type metal mineral mill tailings;
the first auxiliary material can comprise two or more than two of limestone, marble, dolomite and magnesite.
In an exemplary embodiment of the method for preparing a magnesium silicate cement of the present invention, the first predetermined mass ratio of the serpentine mineral-containing raw material to the first auxiliary material may be (60% to 100%): (0% to 40%), wherein the second predetermined mass ratio of the second powder to the second auxiliary material is (70% to 100%): (0% to 30%).
In an exemplary embodiment of the method for preparing a magnesium silicate cement of the present invention, the first powder may include 60% to 100% of a raw material containing serpentine mineral, 0% to 15% of limestone, 0% to 10% of marble, 0% to 20% of dolomite, and 0% to 10% of magnesite, in mass percentage;
the magnesium silicate cementing material can comprise 70 to 100 percent of first powder, 0 to 15 percent of lime, 0 to 15 percent of portland cement clinker, 0 to 30 percent of carbide slag and 0 to 15 percent of gypsum.
In one exemplary embodiment of the method for preparing a magnesium silicate cement of the present invention, the pretreatment includes drying, crushing and pulverizing treatments, wherein the drying temperature may be 80 to 105 ℃; the adsorbed water content in the first powder may be less than 3%.
In an exemplary embodiment of the method for preparing a magnesium silicate cement of the present invention, the drying, crushing and pulverizing processes may be performed under a negative pressure environment having a pressure 5 to 10pa lower than the external atmospheric pressure.
In an exemplary embodiment of the method for preparing a magnesium silicate cement of the present invention, the calcination temperature may be 600 to 1100 ℃, the temperature increase rate may be 3 to 20 ℃/min, and the calcination time may be 5 to 1.5 hours.
In an exemplary embodiment of the method for preparing a magnesium silicate cement according to the present invention, the first powder may have a particle size of 2 mesh or less, and the second powder may have a particle size of 100 mesh or less.
According to another aspect of the present invention, a magnesium silicate gel material is provided, wherein the magnesium silicate gel material is prepared by the above preparation method of a magnesium silicate gel material.
In a further aspect, the invention provides the use of a magnesium silicate cementitious material as described above as a finishing coat or as a wall material formulation.
Compared with the prior art, the beneficial effects of the invention comprise at least one of the following:
(1) The invention takes the rocks, waste rocks and tailings mainly containing serpentine as raw materials to produce the magnesium silicate gel material powder, thereby realizing the resource utilization of various solid wastes, and having important ecological and sustainable development significance for resource protection, saving and high-value utilization;
(2) The recycling of the tailings, the waste rocks and the tailings has important ecological and environmental significance on the safety, environmental protection, reclamation and greenness of the tailings pond;
(3) The novel magnesium silicate gel material powder product is obtained by processing and treating rocks, waste rocks and tailings mainly containing serpentine as raw materials, has the advantages of simple production process, energy conservation and emission reduction, high product added value, low carbon dioxide emission, high ecological environmental benefit and the like, and has important significance for developing new material industry and social economy;
(4) The produced magnesium silicate cementing material powder has the gelling property after being mixed with water, and the formed body is cured into a stone body which has high strength, good stability, no expansion after water absorption, no frost return and strong durability.
Drawings
The above and other objects and/or features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is an SEM image at 1 Kd magnification showing a magnesium silicate cement (obtained by adding water to a powder) according to an exemplary embodiment of a method for producing a magnesium silicate cement of the present invention.
FIG. 2 is an SEM photograph showing a magnesium silicate cement (obtained by adding water to a powder) at a magnification of 10 Kx, according to an exemplary embodiment of the method for producing a magnesium silicate cement of the present invention.
FIG. 3 is an SEM photograph showing another magnesium silicate cement (obtained by adding water to a powder) at a magnification of 1 Kx, according to another exemplary embodiment of the method for producing a magnesium silicate cement of the present invention.
FIG. 4 is an SEM image at 10-thousand times magnification showing another magnesium silicate cement (obtained by adding water to a powder) according to another exemplary embodiment of a method for producing a magnesium silicate cement of the present invention.
Detailed Description
Hereinafter, the magnesium silicate cement of the present invention, and the preparation method and use thereof will be described in detail with reference to the accompanying drawings and exemplary embodiments.
It should be noted that "first," "second," and the like are merely for convenience of description and for ease of distinction, and are not to be construed as indicating or implying relative importance. To those of ordinary skill in the art, some of the term "pressure" herein corresponds to pressure. Plus or minus before the mesh number indicates whether the mesh of the mesh number can be leaked, minus indicates that the mesh of the mesh number can be leaked, namely the particle size is smaller than the mesh size, plus indicates that the mesh of the mesh number cannot be leaked, namely the particle size is larger than the mesh size.
At present, magnesium gel materials represented by magnesium silicate in China have excellent service performance, but the market price of raw materials for preparing the magnesium gel materials is higher, and a large amount of energy consumption is required for producing the raw materials, so that the magnesium gel materials do not accord with the concept of green environmental protection.
Meanwhile, the accumulation of a large amount of domestic serpentine mineral-containing solid wastes brings serious influence and harm to the environment, and the serpentine mineral is an important raw material of the magnesium silicate cementing material, so that a large amount of land resources are occupied while the accumulation of the serpentine mineral is carried out, and idle waste of resources is also caused.
In order to change the current situation, the invention provides a method for preparing a magnesium silicate cementing material by using a serpentine mineral as a raw material of a main component, so as to realize resource utilization of various solid wastes and obtain a novel magnesium silicate cementing material.
In order to achieve the above objects, one aspect of the present invention provides a method for preparing a magnesium silicate gel material.
In one exemplary embodiment of the method for producing a magnesium silicate cement of the present invention, a method for producing a magnesium silicate cement may comprise the steps of:
(1) Mixing a raw material containing serpentine minerals and a first auxiliary material according to a first preset mass ratio, and pretreating to obtain a first powder, wherein the first auxiliary material is at least one of carbonate minerals and carbonate mineral tailings.
The raw material containing serpentine mineral mainly contains serpentine mineral components, and can comprise at least one of serpentine, serpentine mineral separation tailings, chrysotile mineral separation tailings and ultrabasic rock type metal mineral separation tailings.
The first auxiliary material can comprise at least one of carbonate minerals and carbonate mineral tailings, and the carbonate minerals corresponding to the tailings are tailings, leftover materials and the like generated in the ore dressing and production processes. The carbonate mineral comprises calcium-containing or magnesium-containing carbonate mineral.
Further, the first auxiliary material may include two or more of limestone, limestone tailings, marble tailings, dolomite tailings, magnesite, and magnesite tailings.
The first powder contains main minerals and secondary minerals, wherein the main minerals comprise serpentine, talc, calcium carbonate, magnesium carbonate and magnetite, and the secondary minerals comprise chlorite, mica, clay and the like. The first powder density may be 1.12kg/m 3 ～1.5kg/m 3 The adsorbed water content may be less than 3%.
The first predetermined mass ratio includes the case where the first auxiliary material amount is 0, i.e., the first predetermined mass ratio of the raw material containing the serpentine mineral to the first auxiliary material may be 100%:0 percent. In other words, in the step (1), the first powder containing the serpentine mineral can be obtained by directly pretreating the raw material containing the serpentine mineral without adding the first auxiliary material.
When the first adjunct amount is not 0, the first predetermined mass ratio of the serpentine mineral-containing feedstock to the first adjunct can be (60% to 99.9%): (0.01% -40%). If the first predetermined mass ratio of the raw material containing the serpentine mineral to the first auxiliary material is too low (for example, the ratio is 10%: 90%), the national policy of solid waste and resource utilization is not met; if the first predetermined mass ratio of the raw material containing the serpentine mineral to the first auxiliary material is too high (for example, the mixing ratio is 110%: 10%), the physical and chemical properties of the material, such as gelling property, water resistance, etc., are affected. For example, the first predetermined mass ratio of the serpentine mineral containing material to the first excipient may be 61%:40% and 70%:30% and 80%:20%, 90%:10% and 95%:20% and 99.9%:0.01%, etc.
Further, the first powder may include, by mass%, 60% to 100% of a raw material containing a serpentine mineral, 0% to 15% of limestone (or limestone tailings), 0% to 10% of marble (or marble tailings), 0% to 20% of dolomite (or dolomite tailings), and 0% to 10% of magnesite (or magnesite tailings).
The pretreatment comprises drying, crushing and grinding treatment, and the drying temperature can be 80-105 ℃ in the drying process. The adsorbed water content in the first powder may be less than 3%. The adsorption water content of less than 3% is beneficial to the calcination detoxification of the tailings in the subsequent calcination process, and if the adsorption water content exceeds 3%, the heat consumption caused by water evaporation is caused, so that the combustion condition of the first powder in the calcining furnace in the step (2) is influenced.
Further, the drying temperature can be 90-105 ℃; the content of the adsorbed water in the first powder is 1-2%.
In addition, the crushing and grinding can be carried out in a negative pressure environment with the pressure 5-10 pa lower than the external atmospheric pressure, and the external air is not polluted. The negative pressure can let the fresh air of workshop outside flow in, and the dust that contains the asbestos fibre in the workshop discharges fixed place through special dust extraction, can not discharge outside the workshop to reduce environmental pollution. When the negative pressure is more than 10pa, the negative pressure environment can affect the health of staff, and meanwhile, the air flowing speed in a workshop is increased, so that dust is easy to fly, the indoor air cannot be supplemented in time, and the negative pressure environment can be in a slight vacuum state. When the negative pressure is less than 5pa, the negative pressure effect is not good.
The particle size of the first powder obtained after drying, crushing and ball milling can be-325 meshes to-2 meshes. For example, the particle size of the first powder or granule may be-2 mesh, -50 mesh, -100 mesh, -125 mesh, -175 mesh, -245 mesh, -285 mesh, -300 mesh, -325 mesh, or the like. Here, plus sign before the mesh indicates whether the mesh of the mesh can be missed, for example, -2 mesh indicates 2 mesh or less. The particle size of the first powder is controlled within this range, and the obtained magnesium silicate cement can be applied to various fields by adjusting different particle sizes of the product. For example, the magnesium silicate gel material with 325 meshes to-200 meshes can be applied to plastering fine surfaces, and the magnesium silicate gel material with 30 meshes to-2 meshes can be directly used as a material for walling (such as assembled wallboards).
(2) And (3) putting the first powder into a calcining furnace for heating and calcining to obtain a second powder with the main crystal phase of olivine. The air speed and the air quantity need to be controlled in the calcining process, the calcining atmosphere is ensured to be an air atmosphere or an oxygen-containing environment, and the serpentine-containing mineral crystal phase is favorably converted into the forsterite phase in the calcining process. For example, the air speed can be controlled to be 2 m/s-8 m/s in the calcining process to ensure the temperature in the kiln to be stable, and the calcining atmosphere is an air atmosphere or an oxygen-containing environment.
The calcining furnace can comprise a vertical kiln, a rotary kiln, a predecomposition kiln, a suspension kiln and the like, the calcining temperature can be 600-1100 ℃, the heating rate can be 3-20 ℃/min, and the calcining time can be 5-1.5 h. For example, the calcination temperature may be 650 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or the like, the temperature increase rate may be 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min or the like, and the calcination time may be 5min, 15min, 35min, 45min, 60min, 75min, 90min or the like.
If the calcining temperature is lower than 600 ℃ or the calcining time is lower than 5min, the conversion and detoxification of the serpentine-containing minerals cannot be met; when the calcining temperature is more than 1100 ℃, the serpentine-containing mineral starts to sinter and melt under the action of the ingredients, the subsequent utilization value is influenced although the crystalline phase of the serpentine-containing mineral is changed, and meanwhile, a large amount of heat is consumed for high-temperature phase change, so that the energy-saving and environment-friendly requirements are not met; the calcination time is more than 1.5h, and the serpentine-containing minerals are subjected to phase inversion detoxification, so that the calcination time is increased, and energy is wasted.
Preferably, if the temperature rise rate in the calcination process is too low or the calcination time is too long, the production efficiency is low, the production cost is increased, energy waste is caused, and the cycle is prolonged; if the temperature rise rate is too high or the calcination time is too short, the crystal phase transition effect is deteriorated, and the detoxification is insufficient.
The second powder particle with the main crystal phase of olivine comprises the following main chemical components in percentage by mass: 25% -40% of MgO, 35% -40% of SiO 2 、2％～20％CaO、2％～15％Fe 2 O 3 And 2% to 8% of Al 2 O 3 。
The water adding range of the second powder is 15-35%, the second powder has gelling property after being uniformly stirred, and the formed body is cured and solidified into a stone body.
(3) And mixing the second powder particles and a second auxiliary material according to a second preset mass ratio, and grinding to obtain the magnesium silicate gel material, wherein the second auxiliary material is at least one of lime (including quicklime and hydrated lime), carbonate cement clinker, carbide slag, hydrated gypsum and water glass powder.
The second predetermined mass ratio includes a case where the second auxiliary material amount is 0, that is, the second predetermined mass ratio of the second particulate body to the second auxiliary material may be 100%:0 percent. In other words, in step (3), the second powder having olivine as the main crystal phase obtained in step (2) can be directly used as the magnesium silicate gel material of the present invention without adding a second auxiliary material.
When the second auxiliary material amount is not 0, the second predetermined mass ratio of the second particulate matter to the second auxiliary material may be (70% to 99.9%): (0.01% -30%). For example, the second predetermined mass ratio of the second particulate matter to the second auxiliary material may be 70%:30% and 71%:0.01%, 80%:20%, 90%:10% and 95%:5% and 99.9%:0.01%, etc.
If the second predetermined mass ratio of the second powder and the second auxiliary material is too low (for example, the ratio is 50%: 50%), the solid waste dosage is low, and a large amount of ingredients are needed, which is not favorable for realizing the recycling and comprehensive utilization of the solid waste; if the second predetermined mass ratio of the second particulate matter to the second auxiliary material is too high (for example, the ratio is 120%: 10%), the effect of the final product is affected.
Further, the magnesium silicate gel material can comprise 70-100% of first powder, 0-15% of lime, 0-15% of portland cement clinker, 0-30% of carbide slag and 0-15% of gypsum.
The granularity of the second auxiliary material is matched with the granularity of the second powder, and the specific mesh number is-500 meshes to-100 meshes. If the particle size is too large, the flatness and the gelling property are influenced; if the particle size is too small, the cost is high and the mechanical properties are deteriorated. For example, the second auxiliary material may have a particle size of-100 mesh, -125 mesh, -175 mesh, -245 mesh, -285 mesh, -300 mesh, -325 mesh, -360 mesh, -420 mesh, -500 mesh, or the like.
In still another exemplary embodiment of the method for producing a magnesium silicate cement of the present invention, a method for producing a magnesium silicate cement may include the steps of:
(1) Mixing the raw material containing serpentine mineral with a first auxiliary material according to the proportion (60-99.9%): (0.01-40%) and pretreating to obtain the first powder, wherein the first auxiliary material is at least one of carbonate mineral and carbonate mineral tailings.
Further, the first auxiliary material may include two or more of limestone, limestone tailings, marble tailings, dolomite tailings, magnesite, and magnesite tailings.
(2) And (3) putting the first powder into a calcining furnace, heating and calcining to obtain a second powder with the main crystal phase of olivine. Wherein, the calcining temperature can be 600 ℃ to 1100 ℃, the heating rate can be 3 ℃/min to 20 ℃/min, and the calcining time can be 5min to 1.5h. The second powder is a magnesium silicate cementing material.
In still another exemplary embodiment of the method for preparing a magnesium silicate cement of the present invention, a method for preparing a magnesium silicate cement may comprise the steps of:
(1) Pretreating a raw material containing serpentine mineral to obtain first powder.
(2) And (3) putting the first powder into a calcining furnace for heating and calcining to obtain a second powder with the main crystal phase of olivine. Wherein, the calcining temperature can be 600 ℃ to 1100 ℃, the heating rate can be 3 ℃/min to 20 ℃/min, and the calcining time can be 5min to 1.5h.
(3) Mixing the second powder and the second auxiliary material according to the proportion of (70-99.9%): (0.01-30%) and grinding to obtain magnesium silicate gel material, and the second auxiliary material is at least one of lime (including quicklime and hydrated lime), carbonate cement clinker, carbide slag, calcined gypsum and water glass powder.
In another aspect, the present invention provides a magnesium silicate cementitious material.
In an exemplary embodiment of the magnesium silicate cement of the present invention, a magnesium silicate cement is prepared by the method for preparing a magnesium silicate cement as described above.
Compared with the conventional magnesium silicate gel material product, the magnesium silicate gel material product has the following characteristics: the magnesium silicate cementing material product has good water resistance, no collapsibility after long-term soaking, good alkali resistance, uniform consolidation, no obstacle when being scraped and coated, and better bonding strength than gypsum cementing.
In a further aspect, the invention provides the use of a magnesium silicate cementitious material as described above as a finishing coat or as a wall material formulation.
For a better understanding of the above-described exemplary embodiments of the present invention, reference is made to the following description taken in conjunction with the accompanying drawings and detailed description.
Example 1
A method for preparing a magnesium silicate cementitious material may comprise the steps of:
s1, selecting serpentine beneficiation tailings as a raw material containing serpentine minerals, wherein dolomite and marble are used as first auxiliary materials, and the serpentine beneficiation tailings, the dolomite and the marble are mixed according to a mass ratio of 81:10:9, mixing, drying, crushing and ball milling to obtain a first powder body with a grain size of-325 to-200 meshes, wherein the first powder body contains main minerals of serpentine, talc, calcium carbonate, magnesium carbonate and magnetite and secondary minerals of chlorite, mica, clay and the like.
And S2, placing the first powder body obtained in the step S1 into a calcining furnace, and heating and calcining the first powder body for 30min at 800 ℃ to obtain a second powder body with the main crystal phase of olivine.
The second powder particle with the main crystal phase of olivine comprises the following main chemical components in percentage by mass: 27% MgO, 39% SiO 2 、18％CaO、10％Fe 2 O 3 And 6% of Al 2 O 3 . Second powderThe powder body comprises the following components in percentage by mass: water =10:2.2 adding water and stirring uniformly, then having the gelling property, curing and solidifying the formed body into a stone body. The strength of the stone body is 5 MPa-35 MPa, the volume stability is good, the stone body does not expand after absorbing water, frost return is avoided, and the durability is strong.
S3, mixing the second powder and particle obtained in the step S2 with a second auxiliary material according to a mass ratio of 82:18, mixing and grinding to obtain the magnesium silicate gel material powder with the grain diameter of-325 meshes to-200 meshes. The second auxiliary material is carbide slag.
FIG. 1 is an SEM photograph of a magnesium silicate gel (obtained by adding water to a powder) obtained in example 1, magnified 1 Ktimes; FIG. 2 is an SEM photograph of a magnesium silicate gel (obtained by adding water to a powder) obtained in example 1, at a magnification of 10 Ktimes. As can be seen from FIGS. 1 and 2, the microscopic morphology of the test block sample is blocky, and the existence of a uniform petal-shaped aggregate can be found by magnifying the microscopic magnification, so that the test block has better mechanical strength.
Example 2
A method for preparing a magnesium silicate cementitious material may comprise the steps of:
s1, selecting super-basic rock type mineral separation tailings as a raw material containing serpentine minerals, and using marble and magnesite as first auxiliary materials, wherein the super-basic rock type mineral separation tailings, the marble and the magnesite are mixed according to a mass ratio of 85:8:7, mixing, drying, crushing and ball milling to obtain a first powder body with a grain size of-325 meshes to-200 meshes, wherein the first powder body contains main minerals of serpentine, talc, calcium carbonate, magnesium carbonate and magnetite and secondary minerals of chlorite, mica, clay and the like.
And S2, placing the first powder particle obtained in the step S1 into a calcining furnace, and heating and calcining the first powder particle at 850 ℃ for 50min to obtain a second powder particle with the main crystal phase of olivine.
The second powder particle with the main crystal phase of olivine comprises the following main chemical components in percentage by mass: 32% MgO, 41% SiO 2 、13％CaO、9％Fe 2 O 3 And 5% of Al 2 O 3 . The second powder particle comprises the following powder bodies in mass ratio: water =10:1.8 adding water, stirring uniformly, then having gelling property, curing and solidifying the formed body into a stone body. Strength of the stone body is 5MPa to 35MPa, good volume stability, no expansion after water absorption, no frost return and strong durability.
S3, mixing the second powder particle obtained in the step S2 with a second auxiliary material according to a mass ratio of 86:14, mixing and grinding to obtain the magnesium silicate gel material powder with the grain diameter of-200 meshes to-100 meshes. The second auxiliary material is hydrated lime.
FIG. 3 shows an SEM image of another magnesium silicate gel material obtained in example 2 (obtained by adding water to the powder) at a magnification of 1 Ktimes; FIG. 4 shows an SEM image of another magnesium silicate gel material obtained in example 2 (obtained by adding water to the powder) at a magnification of 10 Ktimes. As can be seen from FIGS. 3 and 4, the microscopic morphology of the specimen sample is block-shaped, and the block-shaped body under the high-magnification microscope is formed by uniformly polymerizing petal-shaped bodies.
In summary, the beneficial effects of the invention include at least one of the following:
(1) The invention takes the rocks, waste rocks and tailings mainly containing serpentine as raw materials to produce the magnesium silicate gel material powder, thereby realizing the resource utilization of various solid wastes, and having important ecological and sustainable development significance for resource protection, saving and high-value utilization;
(2) The recycling of the tailings, the waste rocks and the tailings has important ecological and environmental significance on the safety, environmental protection, reclamation and greenness of the tailings pond;
(3) The novel magnesium silicate gel material powder product is obtained by processing and treating rocks, waste rocks and tailings mainly containing serpentine as raw materials, has the advantages of simple production process, energy conservation and emission reduction, high product added value, low carbon dioxide emission, high ecological environmental benefit and the like, and has important significance for developing new material industry and social economy;
(4) The produced magnesium silicate cementing material powder has the gelling property after being mixed with water, and the formed body is cured into a stone body which has high strength, good stability, no expansion after water absorption, no frost return and strong durability.
Although the present invention has been described above in connection with the exemplary embodiments and the accompanying drawings, it will be apparent to those of ordinary skill in the art that various modifications may be made to the above-described embodiments without departing from the spirit and scope of the claims.

Claims (10)

1. The preparation method of the magnesium silicate cementing material is characterized by comprising the following steps of:
mixing a raw material containing serpentine minerals and a first auxiliary material according to a first preset mass ratio, and pretreating to obtain a first powder, wherein the first auxiliary material is at least one of carbonate minerals and carbonate mineral tailings; the first predetermined mass ratio does not include a case where the first amount of the auxiliary material is 0; the raw material containing the serpentine mineral comprises at least one of serpentine, serpentine dressing tailings, chrysotile dressing tailings and super-basic rock type metal mineral dressing tailings; the first powder contains main minerals and secondary minerals, wherein the main minerals comprise serpentine, talc, calcium carbonate, magnesium carbonate and magnetite, and the secondary minerals comprise chlorite, mica and clay;
calcining the first powder to obtain a second powder with the main crystal phase of olivine; the calcining temperature is 600-1100 ℃, and the calcining time is 5 min-1.5 h;
mixing second powder particles and a second auxiliary material according to a second preset mass ratio, and grinding to obtain a magnesium silicate cementing material, wherein the second auxiliary material is at least one of lime, carbonate cement clinker, carbide slag, gypsum and water glass powder; the second predetermined mass ratio includes the case where the second amount of the auxiliary material is 0.
2. The method of producing a magnesium silicate cement according to claim 1,
the first auxiliary material comprises two or more of limestone, marble, dolomite and magnesite.
3. The method for preparing a magnesium silicate cementitious material as claimed in claim 2, characterized in that the first predetermined mass ratio of the raw material containing serpentine mineral to the first auxiliary material is (60-100%): (0% -40%), the second predetermined mass ratio of the second powder to the second auxiliary material is (70% -100%): (0% to 30%).
4. The method for preparing a magnesium silicate cement according to claim 3, wherein the first powder includes 60-100% by mass of a raw material containing serpentine mineral, 0-15% by mass of limestone, 0-10% by mass of marble, 0-20% by mass of dolomitic rock, and 0-10% by mass of magnesite;
the magnesium silicate cementing material comprises 70-100% of first powder, 0-15% of lime, 0-15% of portland cement clinker, 0-30% of carbide slag and 0-15% of gypsum.
5. The method for preparing a magnesium silicate cement according to claim 1, wherein the pretreatment comprises drying, crushing and grinding, wherein the drying temperature is 80-105 ℃; the adsorbed water content in the first powder is less than 3%.
6. The method for producing a magnesium silicate cement according to claim 5, wherein the drying, crushing and pulverizing treatment is performed under a negative pressure environment of 5 to 10pa lower than the atmospheric pressure of the outside.
7. The method for producing a magnesium silicate cement according to claim 1, wherein the temperature rise rate is 3 ℃/min to 20 ℃/min.
8. The method of producing a magnesium silicate cement according to claim 1, wherein the particle size of the first powder is 2 mesh or less, and the particle size of the second powder is 100 mesh or less.
9. A magnesium silicate cement, characterized in that it is produced by the method for producing a magnesium silicate cement according to any one of claims 1 to 8; the magnesium silicate cementing material has the gelatinization property after being stirred by adding water, the strength of a formed body after curing and curing into a stone body is 5MPa to 35MPa, the volume stability is good, the formed body does not expand after absorbing water, frost return is avoided, and the durability is strong.
10. Use of the magnesium silicate cement of claim 9 as a finishing coat or as a formulation for walling.
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