CN115611568B

CN115611568B - Copper tailing-based high-performance concrete and preparation method thereof

Info

Publication number: CN115611568B
Application number: CN202211636209.8A
Authority: CN
Inventors: 朱阳戈; 陈贵斌; 李伟光; 朱雷; 张丹; 刘红丽; 赵庆朝; 李勇; 李学亮; 李泽熙; 许太盛; 高蒙; 方冬晴; 姚迁; 王宇; 沈忱; 马韬
Original assignee: Tongling Nonferrous Metals Group Tongguan Construction And Installation Co ltd; BGRIMM Technology Group Co Ltd
Current assignee: Tongling Nonferrous Metals Group Tongguan Construction And Installation Co ltd; BGRIMM Technology Group Co Ltd
Priority date: 2022-12-20
Filing date: 2022-12-20
Publication date: 2023-04-28
Anticipated expiration: 2042-12-20
Also published as: CN115611568A

Abstract

The application provides copper tailing-based high-performance concrete and a preparation method thereof. The copper tailing-based high-performance concrete comprises the following raw materials in percentage by mass of 100): 15% of cement, 42% of stone, 31% of sand, 5% of fly ash, 0.1% of concrete additive and 6.9% of water; wherein, the sand is partially or completely replaced by copper tailing sand, and the fly ash is partially or completely replaced by copper tailing admixture. The preparation method of the copper tailing-based high-performance concrete comprises the following steps: and mixing the raw materials, and stirring to obtain the copper tailing-based high-performance concrete. The copper tailing-based high-performance concrete provides a new idea for the reduction and comprehensive utilization of copper tailings.

Description

Copper tailing-based high-performance concrete and preparation method thereof

Technical Field

The application relates to the field of solid waste treatment, in particular to copper tailing-based high-performance concrete and a preparation method thereof.

Background

The copper mine has the characteristics of low grade and large tailing yield, most copper tailings have the characteristics of complex components, high sulfur content, fine grain size and the like, the difficulty of large-scale reduction comprehensive utilization is high, and no effective large-scale value-added absorption way exists at present.

The large amount of copper tailings is piled up to cause serious waste of resources, restrict normal production of waste producing enterprises, and bring serious environmental pollution and huge potential safety hazard; meanwhile, concrete is used as a mass building material product which is most widely used, after river sand is forbidden to be mined, the price of important raw material building sand of the concrete is continuously increased, meanwhile, as the thermal power plants in the south of Yangtze river of China are fewer, the coal ash is relatively lacking, the price is continuously increased, the production cost of the concrete is continuously increased due to the continuous increase of the raw material price, and a need for searching new cheap alternative raw materials is urgent.

Therefore, developing the classification and quality replacement of the construction sand and the active mineral admixture in the concrete by the copper tailings, and applying the copper tailings to the concrete by the whole component is an important subject with great application value and social and economic significance. Most of the research in the field still stays in the simple direct incorporation of tailings into concrete at present, and no research on the application of copper tailings to concrete in a graded and graded full component is performed.

Disclosure of Invention

The purpose of the application is to provide copper tailing-based high-performance concrete and a preparation method thereof, so as to solve the problems.

In order to achieve the above purpose, the present application adopts the following technical scheme:

the copper tailing-based high-performance concrete comprises the following raw materials in percentage by mass of 100):

12-15% of cement, 42-46% of stone, 26-31% of sand, 3-5% of fly ash, 0.1-0.3% of concrete admixture and 6-7% of water.

Wherein, the sand is partially or completely replaced by copper tailing sand, and the fly ash is partially or completely replaced by copper tailing admixture;

the copper tailing sand is a particulate matter with the particle size not smaller than 0.15mm, which is obtained by drying, desulfurizing and sorting copper tailings, the copper tailing admixture is obtained by mixing and ball milling copper tailing fine particles and a modified additive, and the copper tailing fine particles are particulate matters with the particle size smaller than 0.15mm, which are obtained by drying, desulfurizing and sorting copper tailings.

Preferably, the modified additive comprises one or more of oleic acid, glacial acetic acid and polyvinyl alcohol.

Preferably, the temperature of the copper tailings is 400-600 ℃.

Preferably, the flue gas obtained by drying the copper tailings is desulfurized to obtain desulfurized gypsum.

Preferably, the desulfurized gypsum is used for preparing a cement retarder.

Preferably, the sand comprises natural sand and/or machine-made sand.

Preferably, the concrete admixture includes a water reducing agent.

Preferably, the water reducing agent comprises one or more of lignosulfonate, aliphatic high efficiency water reducing agent and polycarboxylate type water reducing agent.

Preferably, the mineral composition of the copper tailings comprises quartz, hydrocalumite and limestone.

The application also provides a preparation method of the copper tailing-based high-performance concrete, which comprises the following steps:

and mixing the raw materials, and stirring to obtain the copper tailing-based high-performance concrete.

Compared with the prior art, the beneficial effects of this application include:

aiming at the problems of fine granularity, high sulfur content, high annual output and poor activity of the copper tailings and no effective value-added absorption means, the method for applying the copper tailings to the concrete in a graded and full component manner is provided, and a new thought is provided for the reduction and utilization of the copper tailings. On the other hand, the copper tailings are fine in granularity, and the separated fine-fraction raw materials can meet the fineness requirement of the concrete active mineral admixture through simple grinding, so that the production cost can be greatly reduced; compared with the traditional raw materials, the active mineral admixture prepared from the fine-fraction copper tailings can have stronger micro-aggregate effect, morphological effect and filling effect in concrete, and has the effects of increasing the compressive strength of the concrete and preventing the concrete from cracking.

Aiming at the difficulty that the sulfur-containing copper tailings cannot be directly used as raw materials in the cement concrete industry, synchronous desulfurization is adopted in the process of drying and dehydrating the tailings, and part of sulfur-containing components in the tailings are volatilized into flue gas, so that the sulfur-containing copper tailings can be used in the concrete; aiming at the characteristics of large annual production amount of copper tailings and shortage of raw materials in the concrete industry, a method for using the full-component grading of the copper tailings in concrete is provided; the coarse-grain products (the particles with the grain diameter not smaller than 0.15 mm) obtained by separating the dried and desulfurized copper tailings are used as concrete fine aggregate, and the fine-grain products (the particles with the grain diameter smaller than 0.15 mm) are modified and processed to be used as concrete admixture; the concrete prepared by taking the copper tailings as the main raw material has excellent performance indexes, and provides a new idea for the reduction and comprehensive utilization of the copper tailings.

The preparation method of the copper tailing-based high-performance concrete is simple to operate.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.

Figure 1 is an XRD spectrum of copper tailings.

Detailed Description

The term as used herein:

"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.

When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.

In these examples, the parts and percentages are by mass unless otherwise indicated.

"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.

"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).

12-15% of cement, 42-46% of stones, 26-31% of sand, 3-5% of fly ash, 0.1-0.3% of concrete additive and 6-7% of water;

the copper tailing sand is a particulate matter with the particle size not smaller than 0.15mm, which is obtained by drying and sorting copper tailings, the copper tailing admixture is obtained by mixing and ball milling copper tailing fine particles and a modified additive, and the copper tailing fine particles are particulate matters with the particle size smaller than 0.15mm, which are obtained by drying and sorting copper tailings.

Coarse fraction tailings in the copper tailings can be singly separated to be used as a substitute raw material of building sand, and meanwhile, fine fraction tailings can replace part of concrete active mineral admixture after being processed due to potential pozzolanic activity, so that the micro aggregate effect, filling effect, dilution effect, morphological effect and the like are achieved in the concrete, and the performance of the concrete is enhanced.

Optionally, the cement can be used in the raw materials of the copper tailing-based high-performance concrete in any value of 12%, 13%, 14%, 15% or 12-15%; the use amount of the stones can be 42%, 43%, 44%, 45%, 46% or any value between 42 and 46%; the amount of sand may be 26%, 27%, 28%, 29%, 30%, 31% or any value between 26 and 31%; the dosage of the fly ash can be any value between 3%, 4%, 5% or 3-5%; the dosage of the concrete admixture can be any value between 0.1%, 0.2%, 0.3% or 0.1-0.3%; the water may be used in an amount of 6%, 6.5%, 7% or any value between 6 and 7%.

In an alternative embodiment, the modifying additive comprises one or more of oleic acid, glacial acetic acid, polyvinyl alcohol.

The surface modification of the copper tailings is realized under the non-alkaline condition, and the inert silicon-aluminum components in the copper tailings are activated, so that the volcanic ash activity of the copper tailings is greatly improved.

In an alternative embodiment, the copper tailings are dried at a temperature of 400-600 ℃.

The sulfur-containing minerals in the copper tailings mainly comprise pyrite, pyrrhotite and the like, the main existence forms are FeS, and the sulfur in the FeS volatilizes when the drying temperature reaches about 400 ℃, so that the drying temperature is required to ensure the drying effect of the tailings and reach the volatilization temperature of the sulfur in the tailings.

Optionally, the temperature at which the copper tailings are dried may be 400 ℃, 500 ℃, 600 ℃ or any value between 400 ℃ and 600 ℃.

In an alternative embodiment, the flue gas obtained by drying the copper tailings is desulphurised to obtain desulphurised gypsum.

In an alternative embodiment, the desulfurized gypsum is used to prepare a cement retarder.

In an alternative embodiment, the sand comprises natural sand and/or machine-made sand.

In an alternative embodiment, the concrete admixture includes a water reducing agent.

In an alternative embodiment, the water reducing agent comprises one or more of lignosulfonate, aliphatic high efficiency water reducing agent, and polycarboxylate water reducing agent.

In an alternative embodiment, the mineral composition of the copper tailings includes quartz, hydrocalumite, and limestone.

Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

Example 1

The embodiment provides copper tailing-based high-performance concrete, which comprises the following components in percentage by mass: 15% of cement, 42% of cobble, 31% of copper tailing sand, 5% of copper tailing admixture, 6.9% of water and 0.1% of concrete admixture (BASF polycarboxylate water reducer RHEOPLUS 410).

The preparation method of the copper tailing-based high-performance concrete specifically comprises the following steps:

(1) Firstly, carrying out cylinder-returning drying on copper tailings, carrying out dry type wind power sorting on the copper tailings after drying and desulfurizing, separating out +0.15mm copper tailings sand, and ball-milling the-0.15mm tailings with a modifier to obtain a copper tailings admixture;

the copper tailing raw material contains 15% of water, and the particle size distribution of the copper tailings is shown in table 1; the main mineral components are quartz, hydrocalumite and limestone, the chemical compositions are shown in table 2, and the XRD pattern is shown in figure 1.

TABLE 1 particle size distribution of copper tailings

TABLE 2 copper tailings chemical composition

(2) Mixing copper tailing sand, copper tailing admixture, cement, cobble, concrete admixture and water in proportion, and stirring to obtain the concrete with slump of 185mm, expansion of 455mm and density of 2500kg/m ³ The 3d compressive strength is 23.78Pa and 28d compressive strength is 34.38MPa, the prepared concrete has excellent performance, all indexes meet the requirement of C30 concrete, the single production cost of the prepared concrete is 228 yuan, the concrete is shown in the following table 3, and 900kg of copper tailings can be consumed in each production.

Table 3 example 1 cost table

Example 2

The embodiment provides copper tailing-based high-performance concrete, which comprises the following components in percentage by mass: 15% of cement, 42% of stone, 15% of natural sand, 16% of copper tailing sand, 5% of copper tailing admixture, 6.9% of water and 0.1% of concrete admixture (polycarboxylic acid type high-efficiency water reducer).

(2) Mixing copper tailing sand, copper tailing admixture, cement, cobble, concrete admixture and water in proportion, and stirring to obtain the concrete with slump of 175mm, expansion of 440mm and density of 2460kg/m ³ The 3d compressive strength is 24.78Pa and the 28d compressive strength is 32.38MPa, the prepared concrete has excellent performance, all indexes meet the requirement of C30 concrete, the single production cost of the prepared concrete is 265 yuan, and 525kg of copper tailings can be consumed by producing each concrete.

Example 3

The embodiment provides copper tailing-based high-performance concrete, which comprises the following components in percentage by mass: 15% of cement, 42% of cobble, 31% of copper tailing sand, 2% of fly ash, 3% of copper tailing admixture, 6.9% of water and 0.1% of concrete admixture (polycarboxylic acid type high-efficiency water reducer).

(2) Mixing copper tailing sand, copper tailing admixture, cement, cobble, concrete admixture and water in proportion, and stirring to obtain the concrete with slump of 175mm, expansion of 435mm and density of 2400kg/m ³ The 3d compressive strength is 21.31Pa and the 28d compressive strength is 32.24MPa, the prepared concrete has excellent performance, all indexes meet the requirement of C30 concrete, the single production cost of the prepared concrete is 236 yuan, and 850kg of copper tailings can be consumed by producing each concrete.

Comparative example 1

Mixing cement, construction sand, fly ash, stone, concrete additive and water according to a certain proportion, stirring, and making the concrete slump be 185mm, expansion 455mm and density 2500kg/m ³ The 3d compressive strength is 24.65Pa,28d compressive strength is 35.48MPa, the prepared concrete has excellent performance, each index meets the requirement of C30 concrete, the unilateral production cost of the prepared concrete is about 285 yuan, and the details are shown in the following table 4.

Table 4 comparative example 1 cost table

Comparative example 2

Cement, sand for construction, copper tailings, fly ash, cobble, concrete additive and water are mixed according to a certain proportionMixing and stirring according to a proportion of 15% of cement, 42% of stone, 31% of copper tailing sand, 5% of unmodified copper tailing raw ore, 6.9% of water and 0.1% of concrete additive, wherein the prepared concrete has slump of 140mm, expansion of 370mm and density of 2500kg/m ³ The 3d compressive strength is 19.65MPa, the 28d compressive strength is 27.48MPa, and the prepared concrete cannot meet the index requirement of C30 concrete.

Comparative example 3

Mixing cement, construction sand, copper tailings, fly ash, cobble, concrete additive and water according to a certain proportion, stirring, wherein the preparation proportion is 15% of cement, 42% of cobble, 31% of unfractionated copper tailings sand after pretreatment, 5% of copper tailings additive, 6.9% of water and 0.1% of concrete additive, and the prepared concrete has slump of 270mm, expansion of 520mm and density of 2600kg/m ³ The 3d compressive strength is 20.45MPa, the 28d compressive strength is 28.476MPa, and the prepared concrete cannot meet the index requirement of C30 concrete.

Comparative example 4

Mixing cement, construction sand, copper tailings, fly ash, cobble, concrete additive and water according to a certain proportion, stirring, wherein the preparation proportion is cement 10%, cobble 42%, copper tailings sand 31%, copper tailings additive 10%, water 6.9% and concrete additive 0.1%, and the prepared concrete has slump of 250mm, expansion degree of 480mm and density of 2580kg/m ³ The 3d compressive strength is 17.46MPa, the 28d compressive strength is 21.07MPa, and the prepared concrete can not meet the index requirement of C30 concrete.

According to the copper tailing-based high-performance concrete and the preparation method thereof, the copper tailing graded full component can be applied to concrete, coarse-grain copper tailing sand in copper tailings is used for replacing natural sand which is forbidden to be mined in traditional concrete, fine-grain copper tailing powder is processed to prepare copper tailing admixture which can replace traditional building materials such as fly ash, and production cost of the concrete industry is greatly reduced.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims

1. The preparation method of the copper tailing-based high-performance concrete is characterized by comprising the following steps of:

mixing the raw materials, and stirring to obtain the copper tailing-based high-performance concrete;

the copper tailing-based high-performance concrete comprises the following raw materials in percentage by mass as 100 percent:

wherein the sand is replaced by copper tailing sand, and the fly ash is replaced by copper tailing admixture;

the copper tailing sand is a particulate matter with the particle size not smaller than 0.15mm, which is obtained by drying and sorting copper tailings, the copper tailing admixture is obtained by mixing and ball milling copper tailing fine particles and a modified additive, and the copper tailing fine particles are particulate matters with the particle size smaller than 0.15mm, which are obtained by drying and sorting copper tailings;

the modified additive comprises one or more of oleic acid, glacial acetic acid and polyvinyl alcohol;

the temperature for drying the copper tailings is 400-600 ℃;

the concrete admixture comprises a water reducing agent;

the water reducer comprises one or more of lignosulfonate, aliphatic high-efficiency water reducer and polycarboxylic acid type water reducer;

the mineral composition of the copper tailings comprises quartz, hydrocalumite and limestone;

desulfurizing the flue gas obtained by drying the copper tailings to obtain desulfurized gypsum;

the desulfurized gypsum is used for preparing a cement retarder;

the sand includes natural sand and/or machine-made sand.

2. The preparation method of the copper tailing-based high-performance concrete is characterized by comprising the following steps of:

15% of cement, 42% of stone, 15% of natural sand, 16% of copper tailing sand, 5% of copper tailing admixture, 0.1% of polycarboxylic acid type high-efficiency water reducer and 6.9% of water;

the temperature for drying the copper tailings is 400-600 ℃;

the desulfurized gypsum is used for preparing a cement retarder.

3. The preparation method of the copper tailing-based high-performance concrete is characterized by comprising the following steps of:

15% of cement, 42% of cobble, 31% of copper tailing sand, 2% of fly ash, 3% of copper tailing admixture, 0.1% of polycarboxylic acid type high-efficiency water reducer and 6.9% of water;

the temperature for drying the copper tailings is 400-600 ℃;

the desulfurized gypsum is used for preparing a cement retarder.