CN110845178A - Composite modified enhanced anti-aging tungsten tailing ecological sand-based water permeable brick and preparation method thereof - Google Patents

Composite modified enhanced anti-aging tungsten tailing ecological sand-based water permeable brick and preparation method thereof Download PDF

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Publication number
CN110845178A
CN110845178A CN201911289709.7A CN201911289709A CN110845178A CN 110845178 A CN110845178 A CN 110845178A CN 201911289709 A CN201911289709 A CN 201911289709A CN 110845178 A CN110845178 A CN 110845178A
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epoxy resin
tungsten tailings
water permeable
based water
permeable brick
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Inventor
姜建松
张建强
***
柴天红
刘桂平
马友德
石齐
蔡恒袖
曾亮
揭晓东
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Jiangxi Building Materials Scientific Research & Design Institute
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Jiangxi Building Materials Scientific Research & Design Institute
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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
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/14—Polyepoxides
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017—Aspects relating to the protection of the environment
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00284—Materials permeable to liquids
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2038—Resistance against physical degradation
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/40—Porous or lightweight materials
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention provides an ecological sand-based water permeable brick containing tungsten tailings, which comprises the following components in percentage by weight: 96-97% of film-coated modified tungsten tailings, 2.4-3.2% of composite modified epoxy resin and 0.6-0.8% of epoxy resin curing agent; the film-coated modified tungsten tailings are obtained by modifying siliceous aggregates of tungsten tailings through resin film coating; the composite modified epoxy resin is obtained by carrying out composite doping modification on epoxy resin and a composite modified component comprising an organic surface modifier, inorganic powder and nano superfine oxide. The invention also provides a method for preparing the ecological sand-based water permeable brick containing the tungsten tailings. The water permeable brick has the advantages of low resin consumption, high strength, excellent wear resistance and aging resistance and the like, the preparation method can solve the problem of high cost of preparing the sand-based water permeable brick in southern areas, and can realize the large-scale resource utilization of tungsten tailings.

Description

Composite modified enhanced anti-aging tungsten tailing ecological sand-based water permeable brick and preparation method thereof
Technical Field
The invention relates to the field of building materials, in particular to a water permeable brick, and especially relates to a tungsten tailing ecological sand-based water permeable brick and a preparation method thereof.
Background
The sponge city can also be called as a water elastic city, and is a city structure in which an urban construction system absorbs water, stores water, seeps water and purifies water when raining, and releases and utilizes the stored water when needed, so that rainwater can freely migrate in the city. The construction of water ecological infrastructure is the core of the construction of sponge cities, so that the novel environment-friendly material for the construction of the sponge cities becomes a current research hotspot.
The resin sand-based water permeable brick is an important green novel environment-friendly material for sponge city construction, and is a novel sponge building material with the functions of long water permeable aging, blockage prevention and the like. At present, the resin sand-based water permeable brick is prepared by mixing dried desert aeolian sand (a few of coated desert aeolian sand) serving as siliceous aggregate and epoxy resin and a curing agent serving as a binder and molding in a vibration and pressurization mode. The sand-based water permeable brick also has the problems of large resin consumption, low water permeability coefficient, low strength, poor wear resistance, easy yellowing and aging of resin and high production cost. The wind-laid sand in the washed and dried desert used by the traditional sand-based water permeable brick has the characteristics of round and smooth grain shape, low mud content, high strength and the like, and is an ideal siliceous aggregate. However, the cost for producing the sand-based water permeable bricks in the south is greatly increased due to the regional characteristics that the production areas of raw materials such as the dried desert aeolian sand are concentrated in the north, so that the localization of siliceous aggregates used by the sand-based water permeable bricks is an important cost-reducing and efficiency-improving method for enterprises.
The Jiangxi Gannan region is called tungsten all in the world, the annual discharge amount of tungsten tailings in the whole province is about 690 ten thousand tons, the discharge amount in the Gannan region reaches over 90 percent, the tungsten tailings amount is increased year by year, and the tailings are placed on the ground surface, so that a large amount of land resources are occupied, and great pressure is brought to environmental protection. Therefore, a reasonable utilization way of the tungsten tailings must be found. The tungsten tailings in Jiangxi province are tailings obtained by adopting a physical beneficiation technology, and have the characteristics of fine granularity, high hardness, no chemical reagent residue and chemical composition close to the components of siliceous aggregates required by the sand-based water permeable brick, so that conditions are created for developing the research of the tailings for preparing the sand-based water permeable brick. The use requirements of the sand-based water permeable brick can be met only by simply drying and screening the tungsten tailings.
Based on the above problems commonly existing in the existing sand-based water permeable bricks and the resource utilization requirement of the tungsten tailings, a scheme for preparing the novel high-performance sand-based water permeable brick by using the tungsten tailings in a large amount is necessary to be provided, so that a high-performance building material is provided for the construction of a sponge city, and the resource utilization of the tungsten tailings is realized.
Disclosure of Invention
In view of the above background, the primary object of the present invention is to: the ecological sand-based water permeable brick containing the tungsten tailings has the advantages of low resin consumption, high strength, excellent wear resistance and aging resistance and the like.
Another object of the invention is: the method for preparing the ecological sand-based water permeable brick containing the tungsten tailings can solve the problem of high cost of preparing the sand-based water permeable brick in southern areas, and can realize the large-scale resource utilization of the tungsten tailings.
In order to achieve the purpose, the invention adopts the following technical scheme:
firstly, the invention provides an ecological sand-based water permeable brick containing tungsten tailings, which comprises the following components in percentage by weight: 96-97% of film-coated modified tungsten tailings, 2.4-3.2% of composite modified epoxy resin and 0.6-0.8% of epoxy resin curing agent; the film-coated modified tungsten tailings are obtained by modifying siliceous aggregate of tungsten tailings through resin film coating, and SiO of the tungsten tailings2The content is more than 85 percent, the mud is not contained after washing and drying, and the particle size is 40 to 70 meshes after sieving; the composite modified epoxy resin is obtained by carrying out composite doping modification on epoxy resin and a composite modified component comprising an organic surface modifier, inorganic powder and nano superfine oxide.
In a preferred scheme of the invention, the ecological sand-based water permeable brick containing tungsten tailings comprises the following components in percentage by weight: 96% of the film-coated modified tungsten tailings, 3.2% of the composite modified epoxy resin and 0.8% of the epoxy resin curing agent.
In another preferred scheme of the invention, the ecological sand-based water permeable brick containing tungsten tailings comprises the following components in percentage by weight: 97% of the film-coated modified tungsten tailings, 2.4% of the composite modified epoxy resin and 0.6% of the epoxy resin curing agent.
In another preferred scheme of the invention, the ecological sand-based water permeable brick containing tungsten tailings comprises the following components in percentage by weight: 96.5% of the film-coated modified tungsten tailings, 2.8% of the composite modified epoxy resin and 0.7% of the epoxy resin curing agent.
In the scheme of the invention, the film-coated modified tungsten tailings can be obtained by modifying the siliceous aggregate of the tungsten tailings by a plurality of resin film coating methods; preferably obtained by thermal method resin film coating modification; further preferably, the resin film is modified by the following thermal method: heating the dried tungsten tailings to 210 ℃ of 180-.
In a further preferred embodiment of the present invention, the resin curing agent is selected from methyl etherified high imino melamine or high methyl etherified amino resin 303LF, preferably methyl etherified high imino melamine; the lubricant is selected from calcium stearate, magnesium stearate or barium stearate, and preferably calcium stearate; the silane coupling agent is selected from KH550 silane coupling agent or KH570 silane coupling agent; KH550 silane coupling agents are preferred.
In the preferred scheme of the invention, the compound modified epoxy resin is obtained by compound doping modification of solvent-free epoxy resin and compound modified components comprising organic surface modifier, inorganic powder and nanometer ultrafine oxide; the composite modified component is further preferably composed of an organic surface modifier, inorganic powder, nanometer ultrafine oxide and an anti-aging agent; the organic surface modifier is preferably a silane coupling agent; the inorganic powder is further preferably limestone powder or quartz sand powder; the nanometer superfine oxide is further optimized to be nanometer SiO2Or TiO2(ii) a The anti-aging agent is preferably a light stabilizer and/or an ultraviolet absorber.
In a preferred embodiment of the invention, the composite modified epoxy resin is obtained by composite doping modification of epoxy resin and a composite modified component, and the composite modified component comprises, by weight, 3-5 parts of a silane coupling agent, 2-4 parts of limestone powder and nano SiO21 to 3 portions of light stabilizer, 0.1 to 0.3 portion of ultraviolet absorbent and 0.05 to 0.1 portion of ultraviolet absorbent.
In the scheme of the invention, the epoxy resin curing agent can be various types of epoxy resin curing agents which can be used for hot-method film coating modification; preferred epoxy resin curing agents of the present invention are amine-based epoxy resin curing agents.
On the basis, the invention also provides a method for preparing the ecological sand-based water permeable brick containing the tungsten tailings, which comprises the following steps:
1) carrying out resin film coating modification on the dried tungsten tailings by a thermal method to obtain film-coated modified tungsten tailings;
2) adding a composite modified component into the solvent-free epoxy resin under stirring, and continuously stirring for 120-180s to obtain the composite modified epoxy resin; the composite modified component comprises an organic surface modifier, inorganic powder and a nanometer superfine oxide;
3) adding an epoxy resin curing agent into the composite modified epoxy resin obtained in the step 2), and stirring for 60-90 s;
4) adding the film-coated modified tungsten tailings obtained in the step 1) into the material obtained in the step 3), stirring for 60-90s, and then forming and pressing according to a conventional method to obtain the ecological sand-based water permeable brick containing tungsten tailings.
In a preferred embodiment of the invention, the tungsten tailings of 1) are preferably SiO2The content is more than 85 percent, the tungsten tailings are washed by water, dried and free of mud, and the tungsten tailings are sieved to have the particle size of 40-70 meshes.
In a preferred embodiment of the present invention, the modification of the thermal method resin coating film according to 1) preferably includes the steps of: heating the dried tungsten tailings to 210 ℃ below zero at 180 ℃, adding styrene-acrylic resin accounting for 1.05-1.75% of the mass of the tungsten tailings, mixing and stir-frying for 80-100s, adding a silane coupling agent accounting for 0.6-1.2% of the mass of the styrene-acrylic resin when the temperature of the sand is reduced to 120 ℃ below zero, stirring for 10-20s, adding a resin curing agent accounting for 0.45-0.75% of the mass of the tungsten tailings, stirring for 60-120s, finally adding a lubricant accounting for 3-5% of the mass of the styrene-acrylic resin, stirring for 60-180s, cooling, crushing and sieving to obtain film-coated modified tungsten tailings;
in the preferable scheme of the invention, the addition amount of the 2) composite modification component accounts for 6-13% of the total weight of the 2) solvent-free epoxy resin and the 3) epoxy resin curing agent.
In a further preferred scheme, the composite modified component further contains an anti-aging agent.
In a further preferred embodiment, the organic surface modifier is further preferably a silane coupling agent; the inorganic powder is further preferably limestone powder or quartz sand powder; the nanometer superfine oxide is further optimized to be nanometer SiO2Or TiO2(ii) a The anti-aging agent is preferably a light stabilizer and/or an ultraviolet absorber。
In a further preferred scheme, the composite modified component comprises 3-5 parts by weight of silane coupling agent, 2-4 parts by weight of limestone powder and nano SiO21 to 3 portions of light stabilizer, 0.1 to 0.3 portion of ultraviolet absorbent and 0.05 to 0.1 portion of ultraviolet absorbent.
In a further preferable scheme, the compound modification component added in the step 2) is limestone powder and nano SiO in the proportion2Light stabilizers, ultraviolet absorbers and silane coupling agents.
According to the invention, the performances of the sand-based water permeable brick such as mechanics, wear resistance and aging resistance are improved by carrying out resin coating modification on the tungsten tailing siliceous aggregate and carrying out composite doping modification on the epoxy resin by using the organic surface modifier, the inorganic powder, the nano superfine oxide and the anti-aging agent. The silane coupling agent used for the coating modification of the tungsten tailings and the surface modification of the epoxy resin is a substance with two functional groups with different properties, and the molecular structure of the silane coupling agent is mainly characterized in that molecules contain two groups with different chemical properties, one group is an inorganophilic group and is easy to chemically react with the surface of an inorganic substance; the other is an organophilic group which is capable of chemically reacting with or forming hydrogen bonds soluble in synthetic resins or other polymers. Therefore, the coupling agent is used for improving the interface action between the tungsten tailings and the resin, so that the performances of the modified tungsten tailings and the epoxy resin, such as physical property, electrical property, thermal property, optical property and the like, are greatly improved. The silane coupling agent used in the invention has the functions of reacting with certain groups on the surface of the tungsten tailings and reacting with the epoxy resin, forming an interface layer between the tungsten tailings and the epoxy resin, wherein the interface layer can transfer stress, thereby enhancing the bonding strength between the tungsten tailings and the resin, improving the performance of the water permeable brick, preventing other media from permeating to the interface, improving the interface state, and being beneficial to the improvement of the aging resistance, the stress resistance and the electrical insulation performance of the water permeable brick. The invention uses inorganic powder and nanometer oxide when carrying out composite doping modification on the epoxy resin, and the inorganic powder and the nanometer oxide can play a role in enhancing, toughening and modifying the epoxy resin. In particular nano SiO2The epoxy resin toughening agent has a plurality of special properties, is well bonded with the epoxy resin, and is likely to absorb deformation energy under the action of stress and promote the brittle-tough transformation of the epoxy resin, so that the epoxy resin toughening agent has the effects of strengthening and toughening, and the strength and the ageing resistance of the epoxy resin are greatly improved. In addition, in a preferable scheme of the invention, the anti-aging agents such as light stabilizers, ultraviolet absorbers and the like are selected for the composite doping modification of the epoxy resin, so that the anti-aging performance of the modified resin can be further improved.
Through repeated experiments, the inventor screens out the specific raw material proportion and the process conditions of the modified tungsten tailings and the epoxy resin based on the properties of the raw materials, obtains an ideal modification effect, enables the tungsten tailings to have the performance of replacing desert aeolian sand as siliceous aggregates, and obtains a modified resin material capable of further improving the performance of the water permeable brick. On the basis, the inventor further screens specific raw material mixing ratios for preparing the sand-based water permeable brick based on the properties of various modified materials, and finally obtains ideal effects. In a word, compared with the existing film-coated aeolian sand-based water permeable brick sold in the market, the ecological sand-based water permeable brick containing tungsten tailings has the characteristics of low resin consumption, high strength, excellent wear resistance and aging resistance and low cost. Meanwhile, siliceous aggregate used by the ecological sand-based water permeable brick containing tungsten tailings prepared by the invention is tungsten tailings, so that the problems of insufficient siliceous aggregate and high cost of the sand-based water permeable brick prepared in southern areas are solved, and compared with the film-coated desert aeolian sand purchased in northern areas, the cost of the film-coated tungsten tailings per ton can be reduced by at least 50%; meanwhile, the industrial solid waste of tungsten tailings is greatly consumed and utilized.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
The epoxy resin used in the following examples may be a solvent-free e51 epoxy resin, and the epoxy resin curing agent may be a W93 amine epoxy curing agent, and the curing strength of the epoxy resin can reach 80% of the maximum value within 24 hours under normal temperature conditions.
The silane coupling agent used in the following examples may be KH550 silane coupling agent, colorless transparent liquid, density 0.9510g/cm3The content is more than 98 percent; the density of the limestone powder used is 2.67g/cm3Specific surface area 550m2Per kg, the calcium carbonate content is more than 96 percent; the used nano SiO2SiO 22The content is more than 99.8 percent, the particle size is 15 +/-5 nm, and the specific surface area is 250 +/-30 m2/g。
The light stabilizer used in the following examples may be selected from light stabilizer 770, light stabilizer 944, and the like; the UV absorbers used in the following examples may be selected from UV-531, UV-9 or UVP-327 and the like.
Example 1:
preparing the tungsten tailings with modified coating, which comprises the following steps:
taking tungsten tailings of solid waste, wherein SiO is contained in the tungsten tailings2The content is more than 85 percent, and the mixture is washed, dried and sieved by a 40-70 mesh sieve;
adding the dried and sieved tungsten tailings into a sand mixer, heating to 180 ℃, adding 1.75% by mass of the tungsten tailings of Basff styrene-acrylic resin 671, mixing and stir-frying for 80s, adding 0.6% by mass of a silane coupling agent when the temperature of the sand is reduced to 110 ℃, stirring for 10s, adding 0.75% by mass of the tungsten tailings of cyanote CYMEL325 methyl etherified high imino cyanamide resin curing agent, stirring for 60s, adding 3% by mass of resin of calcium stearate, stirring for 60s, cooling, crushing and sieving to obtain the film-coated modified tungsten tailings I.
Example 2:
preparing the tungsten tailings with modified coating, which comprises the following steps:
taking tungsten tailings of solid waste, wherein SiO is contained in the tungsten tailings2The content is more than 85 percent, and the mixture is washed, dried and sieved by a 40-70 mesh sieve;
adding the dried and sieved tungsten tailings into a sand mixer, heating to 210 ℃, adding 1.05 percent by mass of Basff styrene-acrylic resin 671 into the sand mixer, mixing and stir-frying for 100s, adding 1.2 percent by mass of silane coupling agent into the sand when the temperature of the sand is reduced to 120 ℃, stirring for 20s, adding 0.45 percent by mass of CyTe CYMEL325 methyl etherified high imino cyanamide resin curing agent into the sand mixer, stirring for 120s, adding 5 percent by mass of calcium stearate into the sand mixer, stirring for 180s, cooling, crushing and sieving to obtain the film-coated modified tungsten tailings II.
Example 3:
the preparation method of the ecological sand-based water permeable brick containing tungsten tailings comprises the following steps:
firstly, 300kg of solvent-free e51 epoxy resin is added into a concrete forced mixer, and 15.2kg of limestone powder and 11.4kg of nano SiO are added into the mixer while stirring21.14kg of light stabilizer (770), 0.38kg of ultraviolet absorber and 19kg of silane coupling agent, continuously stirring for 180s to perform composite modification, then adding 80kg of epoxy resin curing agent, stirring for 90s, finally adding 10251kg of the coated tungsten tailings I prepared in example 1, stirring for 90s, uniformly distributing in a mold, and pressing for 5s under the pressure of 20Mpa by using a vibration forming press to obtain the sand-based water permeable brick I.
In percentage by mass, the ecological sand-based water permeable brick containing tungsten tailings prepared in this embodiment contains the following components: 96% of film-coated modified tungsten tailings I, 3.2% of composite modified epoxy resin and 0.8% of epoxy curing agent.
Example 4:
the preparation method of the ecological sand-based water permeable brick containing tungsten tailings comprises the following steps:
firstly, 200kg of solvent-free e51 epoxy resin is added into a concrete forced mixer, and 5.02kg of limestone powder and 2.51kg of nano SiO are added into the mixer while stirring20.25kg of light stabilizer (770), 0.125kg of ultraviolet absorber and 7.53kg of silane coupling agent, continuously stirring for 120s to perform composite modification, then adding 51kg of epoxy resin curing agent, stirring for 60s, finally adding 8600kg of the coated tungsten tailings II prepared in example 2, stirring for 60s, uniformly distributing in a mold, pressing for 3s under 10MPa by using a vibration forming press to obtain the coated tungsten tailings IIAnd the sand-based water permeable brick II.
In percentage by mass, the ecological sand-based water permeable brick containing tungsten tailings prepared in this embodiment contains the following components: 97% of film-coated modified tungsten tailings II, 2.4% of composite modified epoxy resin and 0.6% of epoxy curing agent.
Comparative example 1
A water permeable sand-based brick III was prepared by substantially the same process as in example 3, except that epoxy resin was not subjected to the composite modification described in example 3, but by using the coated tungsten tailings I prepared in example 1 under the same stirring and molding conditions.
Comparative example 2
The resin used in the commercial sand-based water permeable brick is not subjected to composite modification in the invention and is prepared by using the film-coated desert aeolian sand.
Performance detection
The sand-based water permeable bricks of the above examples 3 and 4 and the comparative documents 1 and 2 were used as samples, and the related performance indexes of 7d after the 4 kinds of sand-based water permeable bricks were molded were detected with reference to the JG/T376-2012 "sand-based water permeable brick" standard, and the results are shown in table 1 below.
TABLE 1
Figure 880790DEST_PATH_IMAGE002
As can be seen from table 1 above, the sand-based water permeable brick resin containing tungsten tailings of the present invention has improved compression resistance, fracture resistance, weather resistance and wear resistance compared with the sand-based water permeable bricks prepared from commercially available sand-based water permeable bricks and unmodified resins, and the resin mixing amount and the overall preparation cost are significantly reduced.
The foregoing is considered as illustrative only of the principles, general features and embodiments of the invention, and not as limiting the scope of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. Accordingly, the scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. An ecological sand-based water permeable brick containing tungsten tailings comprises the following components in percentage by weight: 96-97% of film-coated modified tungsten tailings, 2.4-3.2% of composite modified epoxy resin and 0.6-0.8% of epoxy resin curing agent; the film-coated modified tungsten tailings are obtained by modifying siliceous aggregates of tungsten tailings through resin film coating; the composite modified epoxy resin is obtained by carrying out composite doping modification on epoxy resin and a composite modified component comprising an organic surface modifier, inorganic powder and nano superfine oxide.
2. The ecological sand-based water permeable brick containing tungsten tailings of claim 1, wherein the film-coated modified tungsten tailings are obtained by thermally modifying tungsten tailing siliceous aggregates with a resin film; further preferably obtained by the following thermal method resin peritoneal modification: heating the dried tungsten tailings to 210 ℃ of 180-.
3. The ecological sand-based water permeable brick containing tungsten tailings of claim 2, wherein the resin curing agent is selected from methyl etherified high imino melamine or high methyl etherified amino resin 303LF, preferably methyl etherified high imino melamine; the lubricant is selected from calcium stearate, magnesium stearate or barium stearate, and preferably calcium stearate; the silane coupling agent is selected from KH550 silane coupling agent or KH570 silane coupling agent; KH550 silane coupling agents are preferred.
4. The ecological sand-based water permeable material containing tungsten tailings of claim 1The brick is characterized in that the composite modified epoxy resin is obtained by carrying out composite doping modification on solvent-free epoxy resin and a composite modified component comprising an organic surface modifier, inorganic powder and nano superfine oxide; the composite modified component is further preferably composed of an organic surface modifier, inorganic powder, nanometer ultrafine oxide and an anti-aging agent; the organic surface modifier is preferably a silane coupling agent; the inorganic powder is further preferably limestone powder or quartz sand powder; the nanometer superfine oxide is further optimized to be nanometer SiO2Or TiO2(ii) a The anti-aging agent is preferably a light stabilizer and/or an ultraviolet absorber.
5. The ecological sand-based water permeable brick containing tungsten tailings of claim 1, wherein the composite modified epoxy resin is obtained by composite doping modification of epoxy resin and a composite modified component, and the composite modified component comprises 3-5 parts by weight of a silane coupling agent, 2-4 parts by weight of limestone powder and nano SiO in parts by weight21 to 3 portions of light stabilizer, 0.1 to 0.3 portion of ultraviolet absorbent and 0.05 to 0.1 portion of ultraviolet absorbent.
6. The method for preparing the ecological sand-based water permeable brick containing the tungsten tailings of claim 1, comprising the following steps:
1) carrying out resin film coating modification on the dried tungsten tailings by a thermal method to obtain film-coated modified tungsten tailings;
2) adding a composite modified component into the solvent-free epoxy resin under stirring, and continuously stirring for 120-180s to obtain the composite modified epoxy resin; the composite modified component comprises an organic surface modifier, inorganic powder and a nanometer superfine oxide;
3) adding an epoxy resin curing agent into the composite modified epoxy resin obtained in the step 2), and stirring for 60-90 s;
4) adding the film-coated modified tungsten tailings obtained in the step 1) into the material obtained in the step 3), stirring for 60-90s, and then forming and pressing according to a conventional method to obtain the ecological sand-based water permeable brick containing tungsten tailings.
7. The ecological sand-based water permeable brick containing tungsten tailings of claim 6, wherein 1) the thermal method resin coating modification comprises the following steps: heating the dried tungsten tailings to 210 ℃ of 180-.
8. The ecological sand-based water permeable brick containing tungsten tailings of claim 6, wherein 2) the composite modification component is added in an amount of 6-13% of the total weight of 2) the solvent-free epoxy resin and 3) the epoxy resin curing agent; 2) the composite modified component further contains an anti-aging agent.
9. The ecological sand-based water permeable brick containing tungsten tailings of claim 8, wherein the organic surface modifier is selected from silane coupling agents; the inorganic powder is selected from limestone powder or quartz sand powder; the nanometer superfine oxide is selected from nanometer SiO2Or TiO2(ii) a The anti-aging agent is selected from a light stabilizer and/or an ultraviolet absorber.
10. The ecological sand-based water permeable brick containing tungsten tailings of claim 6, wherein 2) the added composite modified component is prepared by sequentially adding 2-4 parts of limestone powder and 1-3 parts of nano SiO20.1-0.3 part of light stabilizer, 0.05-0.1 part of ultraviolet absorbent and 3-5 parts of silane coupling agent.
CN201911289709.7A 2019-12-16 2019-12-16 Composite modified enhanced anti-aging tungsten tailing ecological sand-based water permeable brick and preparation method thereof Pending CN110845178A (en)

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CN111438121A (en) * 2020-04-02 2020-07-24 曹银花 Processing method for preparing raw materials of polymer concrete ecological water permeable brick
CN112645684A (en) * 2020-12-22 2021-04-13 南昌大学 Method for preparing ceramic sintered water permeable brick from tungsten tailings
CN115259745A (en) * 2022-05-23 2022-11-01 浙江玖隆新材料科技有限公司 Manufacturing process and formula of water permeable brick
CN115849754A (en) * 2022-11-11 2023-03-28 华润水泥技术研发有限公司 Superfine tungsten tailing filler and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN115849754B (en) * 2022-11-11 2023-11-21 华润水泥技术研发有限公司 Superfine tungsten tailing filling material and preparation method thereof

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