CN112374788A - Tungsten tailing based composite admixture for concrete and preparation method thereof - Google Patents
Tungsten tailing based composite admixture for concrete and preparation method thereof Download PDFInfo
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- CN112374788A CN112374788A CN202011095127.8A CN202011095127A CN112374788A CN 112374788 A CN112374788 A CN 112374788A CN 202011095127 A CN202011095127 A CN 202011095127A CN 112374788 A CN112374788 A CN 112374788A
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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Abstract
The invention provides a tungsten tailing based composite admixture for concrete, which is prepared from the following raw materials in parts by weight: 10-15 parts of limestone chips, 10-15 parts of fly ash, 10-15 parts of slag powder, 60-70 parts of tungsten tailings and 0.05 part of excitation modified material; wherein the excitation modified material further comprises 25-35% of triethanolamine, 20-33% of triisopropanolamine and 34-50% of diethanol monoisopropanolamine by mass percentage. The invention also provides a method for preparing the tungsten tailing based composite admixture for concrete. The composite admixture can completely replace class II fly ash and partially replace class S95 mineral powder in concrete, improves the workability of the concrete, and improves the strength, durability and long-term stability of the concrete.
Description
Technical Field
The invention relates to the field of concrete, in particular to a tungsten tailing based composite admixture with certain activity for preparing concrete.
Background
At present, the fly ash as the most important variety of mineral admixture for concrete is accepted by academic and engineering circles and is widely used. However, because of the shortage of high-quality fly ash resources, the fly ash of more than two grades can not meet the supply requirements. The slag powder has high cost and high concrete hydration temperature. Therefore, under the conditions that the price of cement is continuously increased and the coal ash resource is in shortage, a novel mineral admixture is required to be searched for to supplement the coal ash.
The tungsten tailings are solid wastes generated in the beneficiation process of tungsten ores, and the tungsten ores are generally low in grade, so that the proportion of the tailings generated in the beneficiation process is very large. At present, tungsten tailings are not effectively utilized integrally, and are mainly stored in a tailing pond or backfilled into a mine, so that resource waste is caused, land is occupied, the environment is polluted, and human health is harmed. However, the tungsten tailings mainly comprise oxides of silicon and aluminum, contain calcium, are fine in particles, and have natural advantages when being used for building materials.
In order to solve the above two problems, that is, the use of fly ash in concrete is reduced, and the overall utilization rate of tungsten tailings is improved, researchers have proposed various schemes for preparing concrete admixtures by using tungsten tailings, for example, patent document CN103288371A discloses a tungsten tailing concrete admixture which is composed of tungsten tailings, quicklime, gypsum, mirabilite and the like, and is obtained by milling with a ball mill, in the scheme, only by the physical activation of milling, the obtained admixture is insufficient in activity; (ii) a CN107417214A discloses a tungsten tailing admixture concrete, wherein an active ultrafine powder admixture is obtained by mixing and grinding tungsten tailings and high-magnesium limestone, the grinding process of the admixture in the preparation process needs to consume larger energy, and the admixture cannot obtain enough activity by simple physical grinding; CN110128042A discloses a process for preparing cement active mixed materials and concrete admixtures from tungsten tailings, wherein the tungsten tailings are sieved, coarse tailings are used as concrete admixtures, fine tailings powder is dried and then mixed with a polycarboxylate alcohol amine type polymer activator to obtain cement active mixed materials, and the concrete admixtures and the cement active mixed materials obtained by the above scheme hardly have sufficient activity. In a word, the existing schemes do not relate to the problem of how to solve the replacement of the fly ash, and the tungsten tailing admixture cannot have enough ideal activity and is difficult to replace the fly ash.
Therefore, there is a need to provide a new concrete admixture using tungsten tailings, which has activity enough to replace fly ash, so as to solve the environmental problem caused by tungsten tailings accumulation and the problem of insufficient yield of admixtures such as fly ash.
Disclosure of Invention
The invention aims to: a tungsten tailing based composite admixture capable of completely replacing fly ash to be used for concrete, and aims to solve the problems that a grinding system is high in power consumption when the tungsten tailing based composite admixture is prepared, and the activity index is insufficient when the tungsten tailing based composite admixture is used for concrete.
The invention realizes the aim through the following technical scheme:
firstly, providing a tungsten tailing based composite admixture for concrete, which is prepared from the following raw materials in parts by weight: 10-15 parts of limestone chips, 10-15 parts of fly ash, 10-15 parts of slag powder, 60-70 parts of tungsten tailings and 0.05 part of excitation modified material, wherein the excitation modified material further comprises 25-35% of triethanolamine, 20-33% of triisopropanolamine and 34-50% of diethanol monoisopropanolamine in percentage by mass.
In a preferred scheme of the invention, the tungsten tailing based composite admixture is prepared from the following raw materials in parts by weight: 10-15 parts of limestone chips, 10-15 parts of fly ash, 10-15 parts of slag powder, 60-70 parts of tungsten tailings and 0.05 part of excitation modified material, wherein the excitation modified material further comprises 31-33% of triethanolamine, 24-33% of triisopropanolamine and 34-45% of diethanol monoisopropanolamine in percentage by mass.
In a more preferable scheme of the invention, the tungsten tailing based composite admixture is prepared from the following raw materials in parts by weight: 10 parts of limestone chips, 10 parts of fly ash, 10 parts of slag powder, 70 parts of tungsten tailings and 0.05 part of excitation modified material, wherein the excitation modified material further comprises 33% of triethanolamine, 33% of triisopropanolamine and 34% of diethanol monoisopropanolamine in percentage by mass.
In another more preferable scheme of the invention, the tungsten tailing based composite admixture is prepared from the following raw materials in parts by weight: 10 parts of limestone chips, 15 parts of fly ash, 15 parts of slag powder, 60 parts of tungsten tailings and 0.05 part of excitation modified material, wherein the excitation modified material further comprises 31% of triethanolamine, 24% of triisopropanolamine and 45% of diethanol monoisopropanolamine in percentage by mass.
In the preferable scheme of the invention, the particle size of the limestone chips is 2.36-4.75mm, the content of stone powder is less than 2%, the MB value is less than 0.50, and the content of calcium carbonate is more than 90%. The particle size of the limestone fragments mainly influences grinding parameters and is directly related to the energy consumption of grinding the composite admixture; the working performance of concrete is influenced by the content of stone powder and the MB value, the content of stone powder is too high, and when the MB value is more than 1.4, the fine particles have a large amount of soil components, so that the slump loss of concrete is too high; limestone fines used to make composite admixtures require a certain degree of purity, i.e., calcium carbonate content.
In a preferable scheme of the invention, the maximum particle size of the tungsten tailings is not more than 2.36 mm. Because the grindability of the tungsten tailings is poor, the grain size of the fed materials directly influences the energy consumption in the grinding process.
In a preferable scheme of the invention, the loss on ignition of the fly ash is not more than 8%.
In a preferred embodiment of the invention, the slag powder has a 28d activity index value of not less than 95%.
On the basis, the invention also provides a method for preparing the tungsten tailing based composite admixture for concrete, which comprises the following steps:
according to the weight portion, 60-70 portions of tungsten tailings, 10-15 portions of limestone fragments and 0.05 portion of excitation modified material are jointly ground for 20-40min by a ball mill under the condition that the rotating speed is 45-50r/min, and the Bosch's specific surface area after grinding is controlled at 500-700m2Kg, the excitation modified material is prepared from the following components in percentage by massThe composition consists of 25 to 35 percent of triethanolamine, 20 to 33 percent of triisopropanolamine and 34 to 50 percent of diethanol monoisopropanolamine; then adding 10-15 parts of fly ash and 10-15 parts of slag powder, and homogenizing to obtain the tungsten tailing based composite admixture for concrete.
The tungsten tailing based composite admixture is powder prepared by mixing tungsten tailings and limestone chips serving as main raw materials and then adding fly ash and slag powder through a certain grinding process. In the prior art, because the tungsten tailings have poor wear resistance, a certain amount of stone chips are required to be mixed and ground together, so that the limitation of poor wear resistance of the tungsten tailings can be overcome. However, experiments show that the activity of the admixture is still required to be further improved while the grinding problem is overcome, so that the novel green tailing composite admixture (tungsten tailing based composite modified mineral admixture) is prepared by double excitation modification of mechanical force ultrafine grinding and additional organic chemical surface modification, the compatibility of the novel green tailing composite admixture with an admixture is improved, the hydration activity of the novel green tailing composite modified mineral admixture is improved, the novel green tailing composite modified mineral admixture is successfully applied to premixed concrete, and the workability, the mechanical property and the durability of the premixed concrete are obviously improved.
Compared with the tungsten tailing concrete admixture in the prior art, the admixture has the following beneficial effects:
1. the tungsten tailing based composite admixture for concrete can completely replace class II fly ash and partially replace class S95 mineral powder in concrete, improves the workability of the concrete, and improves the strength, durability and long-term stability of the concrete.
2. According to the invention, functional modified excitation materials are added into the tungsten tailings, the fly ash and the slag powder, and double modification of mechanical force ultrafine grinding and chemical excitation is carried out, so that the grinding efficiency of the product can be improved, and the strength of the concrete can be ensured when the product is doped into the concrete.
3. The method of the invention obviously improves the workability of the concrete and increases the expansion degree of the concrete under the condition of the same slump.
In a word, aiming at the problems that the tungsten tailings are poor in grindability, the composite admixture is low in activity, poor in compatibility with a polycarboxylic acid water reducing agent and difficult to apply to concrete, the tungsten tailings-based composite admixture is obtained by adding a modification material and a functional material and using a physical and chemical method. The composite admixture of the invention utilizes a large amount of industrial tailings, reduces the stacking of the industrial tailings, relieves the pressure of environmental pollution and land resources, can completely replace secondary fly ash or part of mineral powder, has the maximum use amount of 40 percent of cementing materials, has lower product price than the secondary fly ash in the market, and has remarkable social, environmental and economic benefits.
Detailed Description
In order to better understand the invention, the following examples further illustrate the content of the invention, but the content of the invention is not limited to the following examples, and the examples should not be construed as limiting the invention.
Example 1:
the preparation method of the tungsten tailing based composite admixture for concrete comprises the following steps:
putting 70 parts of tungsten tailings, 10 parts of limestone fragments and 0.05 part of excitation modifier into a planetary ball mill for grinding together in parts by mass, grinding for 28min under the condition that the rotating speed is 45-50r/min, and controlling the Bosch specific surface area after grinding to be 500-600 m-2And/kg, and then blending and homogenizing with 10 parts of fly ash and 10 parts of slag powder to obtain the tungsten tailing based composite admixture. The excitation modifier comprises 33% of triethanolamine, 33% of triisopropanolamine and 34% of diethanolisopropanolamine by mass percentage.
Example 2:
the preparation method of the tungsten tailing based composite admixture for concrete comprises the following steps:
putting 60 parts of tungsten tailings, 10 parts of limestone fragments and 0.05 part of excitation modifier into a planetary ball mill for grinding together in parts by mass, grinding for 38min under the condition that the rotating speed is 45-50r/min, and controlling the Bosch specific surface area after grinding to be 600-700 m-2And/kg, and then blending and homogenizing with 15 parts of fly ash and 15 parts of slag powder to obtain the tungsten tailing based composite admixture. The excitation modifier comprises 31% of triethanolamine, 24% of triisopropanolamine and 45% of diethanol monoisopropanolamine by mass percentage.
The above examples 1 and 2 are applied to cement mortar and C30 concrete respectively, and the related performance indexes of mortar and concrete doped with the above two composite admixtures are detected respectively by referring to the standards such as JGJ 55-2011 "design rule for mix proportion of common concrete", and the results are shown in tables 1 and 2 respectively.
TABLE 1 correlation of properties of cement mortars incorporating the tungsten tailing based composite admixtures of the present invention
TABLE 2 relevant Properties of C30 concrete doped with the tungsten tailing based composite admixture according to the invention
In summary, the composite admixture prepared by the above embodiments of the present invention has various technical index values in accordance with JG/T486-2Kg, angle of repose is less than or equal to 45 degrees; the 28d activity index of the cement mortar doped with the tungsten tailing based composite admixture is more than or equal to 80 percent; after the tungsten tailing based composite admixture is used for replacing fly ash in concrete, the strength of the admixture is not lower than 95% of that of the prior standard concrete.
Claims (10)
1. The tungsten tailing based composite admixture for concrete is prepared from the following raw materials in parts by weight: 10-15 parts of limestone chips, 10-15 parts of fly ash, 10-15 parts of slag powder, 60-70 parts of tungsten tailings and 0.05 part of excitation modified material; wherein the excitation modified material further comprises 25-35% of triethanolamine, 20-33% of triisopropanolamine and 34-50% of diethanol monoisopropanolamine by mass percentage.
2. The tungsten tailing based composite admixture as defined in claim 1, wherein the excitation modified material comprises 31-33% triethanolamine, 24-33% triisopropanolamine and 34-45% diethanolisopropanolamine by mass percentage.
3. The tungsten tailing based composite admixture according to any one of the claims 1 or 2, which is characterized by being prepared from the following raw materials in parts by weight: 10 parts of limestone chips, 10 parts of fly ash, 10 parts of slag powder, 70 parts of tungsten tailings and 0.05 part of excitation modified material; wherein the excitation modified material further comprises 33 percent of triethanolamine, 33 percent of triisopropanolamine and 34 percent of diethanolisopropanolamine by mass percentage.
4. The tungsten tailing based composite admixture according to any one of the claims 1 or 2, which is characterized by being prepared from the following raw materials in parts by weight: 10 parts of limestone chips, 15 parts of fly ash, 15 parts of slag powder, 60 parts of tungsten tailings and 0.05 part of excitation modified material; wherein the excitation modified material further comprises 31 percent of triethanolamine, 24 percent of triisopropanolamine and 45 percent of diethanol monoisopropanolamine by mass percentage.
5. The tungsten tailing based composite admixture according to claim 1, wherein the particle size of the limestone chips is 2.36-4.75mm, the mud content is less than 2%, the MB value is less than 0.50, and the calcium carbonate content is more than 90%.
6. The tungsten tailing based composite admixture according to claim 1, wherein the maximum particle size of the tungsten tailings is not more than 2.36 mm.
7. The tungsten tailing based composite admixture according to claim 1, wherein the loss on ignition of the fly ash is not more than 8%.
8. The tungsten tailing based composite admixture as defined in claim 1, wherein the Boehringer specific surface area of the tungsten tailing based composite admixture is 500-700m2/kg。
9. The tungsten tailing based composite admixture according to claim 1,the preparation method is characterized in that the composite admixture is prepared by the following steps: grinding the tungsten tailings, the limestone fragments and the excitation modified material together for 20-40min by using a ball mill at the rotating speed of 45-50r/min according to the proportion, and controlling the Bosch specific surface area after grinding to be 500-700m2And/kg, then adding the fly ash and the slag powder in the proportion, and homogenizing to obtain the tungsten tailing based composite admixture for concrete.
10. A method of preparing a tungsten tailings based composite admixture for concrete comprising: according to the weight portion, 60-70 portions of tungsten tailings, 10-15 portions of limestone fragments and 0.05 portion of excitation modified material are jointly ground for 20-40min by a ball mill under the condition that the rotating speed is 45-50r/min, and the Bosch's specific surface area after grinding is controlled at 500-700m2The excitation modified material comprises 25-35% of triethanolamine, 20-33% of triisopropanolamine and 34-50% of diethanol monoisopropanolamine by mass percent; then adding 10-15 parts of fly ash and 10-15 parts of slag powder, and homogenizing to obtain the tungsten tailing based composite admixture for concrete.
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| CN115959860A (en) * | 2022-11-30 | 2023-04-14 | 华润水泥技术研发有限公司 | Tungsten tailing high-performance admixture for concrete and preparation method thereof |
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