CN111635149A

CN111635149A - Treatment method of copper slag, baking-free water-permeable material and manufacturing method thereof

Info

Publication number: CN111635149A
Application number: CN202010513826.3A
Authority: CN
Inventors: 代文彬; 郭亚光; 苟海鹏; 吕东
Original assignee: China ENFI Engineering Corp
Current assignee: China ENFI Engineering Corp
Priority date: 2020-06-08
Filing date: 2020-06-08
Publication date: 2020-09-08
Anticipated expiration: 2040-06-08
Also published as: CN111635149B

Abstract

The invention provides a copper slag treatment method, a baking-free water-permeable material and a manufacturing method thereof. The processing method comprises the following steps: carrying out reduction smelting on the copper slag to obtain valuable metal and reduction slag; cooling the slag to 200-300 ℃ to obtain tailings, wherein the cooling rate of the tailings at 650-1100 ℃ is less than or equal to 50 ℃/min. After the copper slag is subjected to the secondary reduction smelting process, the temperature of the reduction slag is usually more than 1400 ℃. After the reduction slag is discharged, the reduction slag is slowly cooled at a specific cooling rate, so that the molten tailings can be sufficiently crystallized. On the one hand, the solidified tailings can be harder in texture, and the defects of bubbles, pores, cracks and the like in the tailings are reduced, and on the other hand, the solidified tailings can also play a role in solidifying and stabilizing residual heavy metal elements in the residual tailings, so that the residual heavy metal elements are prevented from being leached to pollute a water source. The treatment method has the advantages of simple process, low cost, good environmental protection and the like.

Description

Treatment method of copper slag, baking-free water-permeable material and manufacturing method thereof

Technical Field

The invention relates to the field of ore smelting, in particular to a copper slag treatment method, a baking-free permeable material and a manufacturing method thereof.

Background

The permeable road surface can adjust water resource environments such as urban rainwater, green water, underground water, river and lake water and the like, reduces the pressure of a municipal drainage system, and has the functions of flood control and drainage. The permeable pavement can increase the air permeability of the atmosphere and the underground, can improve the heat exchange process of the road and the environment by means of the evaporation effect of the surface moisture of the pavement, adjust the surface temperature of the city, improve the local climate, further reduce the effect of the city heat island, and has important significance for city energy conservation and water conservation. Therefore, development of low-cost, energy-saving and harmless permeable materials gradually becomes a hotspot, wherein various solid waste materials are directly utilized for development, and the most remarkable effects of reducing exploitation of natural resources, reducing environmental pollution, lightening social burden and the like are achieved.

The copper slag is solid waste slag obtained after copper ore is subjected to a series of pyrometallurgy. Generally, because of the low grade of the residual copper, the copper is difficult to recover, and most of the copper is directly discarded, or is stacked outside a dump or sold for part of the building material industry. In the copper slag, there still remain noble metal elements such as copper, iron, gold, and silver, but these valuable metal elements are not sufficiently recovered, and the loss is serious. The residual valuable metal elements in the copper slag are fully recovered, so that the economic benefit can be improved, and the problem caused by copper slag accumulation can be solved. Therefore, the copper slag is directly subjected to secondary melting reduction under the action of a reducing agent and high temperature, and the recovery of the valuable elements in the copper slag can be realized. And the residual secondary reduction tailings are also good building material raw materials.

At present, the secondary reduction smelting of copper slag is still in the research and development stage, and large-scale engineering application is gradually promoted. The research on recycling of the secondary reduction copper slag needs to be followed in time, and a new secondary reduction process can be matched at the same time, so that the slag-free production of a metallurgical plant is realized.

The prior document (CN108129083A) provides a method for preparing a water-permeable material by using the residual tailings after copper slag is subjected to magnetic separation. Part of tailings are used as cementing materials after being ground with fly ash and blast furnace slag, and the rest tailings are used as aggregates after being pelletized with bentonite. Finally, the two are mixed, stirred, filled in a mold, demoulded and then subjected to microwave curing to obtain the product. Although the document proposes a method for preparing the water permeable material by using the copper tailings, the copper tailings still need to be calcined, so that the method has the defects of high energy consumption, high cost and the like.

In the prior document (CN103553392B), copper slag is directly subjected to microwave activation for 2-4 min and then ground to a comparative area of 420m²Kg, used as cement admixture. The composite Portland cement is prepared by mixing 10-30% of copper slag mixed material and 4% of desulfurized gypsum into ordinary Portland cement uniformly, and the performance reaches 52.5 strength grade. The method needs to firstly perform microwave activation on the copper tailings, but the method has the problems of large investment, high power consumption, high cost and the like due to the large amount of the tailings, the scarcity of large-scale microwave equipment and the complex structure of the equipment.

The prior document (CN106673418A) provides a method for preparing mineral wool from copper slag. It includes: carrying out reduction-melting separation on the copper slag to extract iron, and obtaining residual tailings and an iron-containing extract; mixing and melting the residual tailings and the modifying agent, preparing fibers by a centrifugal machine and an air blast action, and adding a binder to prepare mineral wool serving as a heat-resistant heat-preservation and heat-insulation material. The method needs to perform secondary melting after tempering the tailings, and the melting and fiber forming equipment has large investment, complex process control, high energy consumption of products and higher cost.

The prior document (CN105271958B) provides a method for producing aerated concrete from copper tailings. It includes: firstly, levigating and pulping water-quenched copper slag generated by a smelting plant to obtain slurry; performing flotation secondary copper separation on the slurry to obtain flotation slag and copper-containing materials; then sending the flotation slag into a rotary kiln for high-temperature reduction roasting to obtain a roasted product; and finally, carrying out magnetic separation on the roasted product to extract iron, thereby obtaining copper tailings. And mixing the copper tailing pulp with lime slurry, silica sand, cement and the like, adding an aluminum powder foaming agent, performing injection molding and standing foaming, performing autoclaved curing, and cutting to obtain the aerated concrete. Although the method firstly extracts the residual copper and iron elements from the copper slag for the second time and then uses the residual copper slag to prepare the aerated concrete, the method has the defects of long whole process flow, multiple working procedures, large amount of waste water, high consumption of metal aluminum powder and high price, and thus the method has the defects of high process processing cost, high enterprise investment and the like.

In view of the above problems, there is a need to provide a method for treating copper slag with simple process and low cost.

Disclosure of Invention

The invention mainly aims to provide a copper slag treatment method, a baking-free water-permeable material and a manufacturing method thereof, and aims to solve the problems of complex process and high cost of the existing copper slag treatment method.

In order to achieve the above object, according to an aspect of the present invention, there is provided a method of treating copper slag, the method comprising: carrying out reduction smelting on the copper slag to obtain valuable metal and reduction slag; cooling the slag to be less than or equal to 500 ℃ to obtain tailings, wherein the cooling rate of the tailings at 650-1100 ℃ is less than or equal to 50 ℃/min.

Furthermore, the cooling rate of the tailings at 650-1100 ℃ is 10-25 ℃/min.

Further, the temperature of reduction smelting is 1350-1500 ℃.

Another aspect of the present application further provides a manufacturing method of a baking-free water-permeable material, including: crushing and carrying out first screening treatment on the tailings obtained by the treatment method to obtain aggregate, wherein the granularity of the aggregate is 2.4-10 mm; and mixing the aggregate, the cementing material and water, and sequentially carrying out injection molding, demolding and curing treatment to obtain the baking-free permeable material.

Further, the manufacturing method further includes: carrying out second screening treatment on the aggregate to obtain fine aggregate and coarse aggregate, wherein the granularity of the fine aggregate is 2.4-4.75 mm, and the granularity of the coarse aggregate is 4.76-10 mm; mixing fine aggregate and/or coarse aggregate, the cementing material and water, and then sequentially carrying out injection molding, demolding and curing treatment to obtain the baking-free water-permeable material.

Further, when the aggregate is fine aggregate, the weight ratio of the fine aggregate, the cementing material and the water is (22-32): (6-12): (2-8); when the aggregate is coarse aggregate, the weight ratio of the coarse aggregate to the cementing material to the water is (20-36): (4-15): (2-10); when the aggregate is a mixture of fine aggregate and coarse aggregate, the weight ratio of the coarse aggregate to the fine aggregate to the cementing material to the water is (14-22) to (8-18) to (10-20) to (2-10).

Further, the cementitious material is selected from one or more of the group consisting of portland cement, ordinary portland cement, portland slag cement, pozzolanic portland cement, fly ash portland cement, and composite portland cement.

Further, the curing process is selected from natural water spraying curing, steam curing or steam pressure curing; preferably, the time of natural water spraying maintenance is more than or equal to 28 days; the steam curing time is 24-72 h; the temperature of the steam pressure curing is 150-180 ℃, and the steam pressure time is 10-24 h.

Further, the manufacturing method further includes: adding a water reducing agent and an optional pigment in the mixing process of the aggregate, the cementing material and the water; preferably, the pigment is an iron oxide based pigment, more preferably red, blue, yellow or black iron oxide.

Furthermore, the pigment accounts for 2-8% of the weight of the cementing material.

The application further provides a baking-free water-permeable material, the raw materials for preparing the baking-free water-permeable material comprise tailings obtained by the processing method, and/or the baking-free water-permeable material is prepared by the manufacturing method.

By applying the technical scheme of the invention, after the copper slag is subjected to the secondary reduction smelting process, the temperature of the reduction slag is usually more than 1400 ℃. After the reduction slag is discharged, the reduction slag is slowly cooled at a specific cooling rate, so that the molten tailings can be sufficiently crystallized. On the one hand, the solidified tailings can be harder in texture, and the defects of bubbles, pores, cracks and the like in the tailings are reduced, and on the other hand, the solidified tailings can also play a role in solidifying and stabilizing residual heavy metal elements in the residual tailings, so that the residual heavy metal elements are prevented from being leached to pollute a water source. The treatment method has the advantages of simple process, low cost, good environmental protection and the like.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:

fig. 1 shows a schematic view of a preferred process for the preparation of a water permeable material according to the present invention.

Detailed Description

As mentioned in the background art, the existing copper slag treatment method has the problems of complex process and high cost. In order to solve the technical problem, the application provides a method for treating copper slag, which comprises the following steps: carrying out reduction smelting on the copper slag to obtain valuable metal and reduction slag; and cooling the reduction slag to be less than or equal to 500 ℃ to obtain tailings, wherein the cooling rate of the tailings at 650-1100 ℃ is less than or equal to 50 ℃/min in the cooling process.

After the copper slag is subjected to the secondary reduction smelting process, the temperature of the reduction slag is usually more than 1400 ℃. After the reduction slag is discharged, the reduction slag is slowly cooled at a specific cooling rate, so that the molten tailings can be sufficiently crystallized. On the one hand, the solidified tailings can be harder in texture, and the defects of bubbles, pores, cracks and the like in the tailings are reduced, and on the other hand, the solidified tailings can also play a role in solidifying and stabilizing residual heavy metal elements in the residual tailings, so that the residual heavy metal elements are prevented from being leached to pollute a water source. The treatment method has the advantages of simple process, low cost, good environmental protection and the like.

Preferably, the tailings are slowly cooled in the cooling process, and the molten tailings can be poured into a special slag pit, a slag ladle, a slag basin or other containers capable of containing liquid slag, the container is covered with a cover for heat preservation, and the molten tailings are taken out after being cooled to a target temperature and then are treated.

In order to further improve the comprehensive performance of the copper slag and further improve the subsequent application performance of the copper slag, in a preferred embodiment, the cooling rate of the tailings at 650-1100 ℃ is 10-25 ℃/min in the cooling process.

In a preferred embodiment, the temperature of the reduction smelting is 1350-1500 ℃. Limiting the melting temperature to the above range is advantageous in further reducing the content of valuable metal elements in the reduced slag, as compared to other ranges.

Another aspect of the present application further provides a manufacturing method of a baking-free water-permeable material, including: crushing and carrying out first screening treatment on the tailings obtained by the treatment method to obtain aggregate, wherein the granularity of the aggregate is 2.4-10 mm; and mixing the aggregate, the cementing material and water, and sequentially carrying out injection molding, demolding and curing treatment to obtain the baking-free water-permeable material.

By adopting the method, the tailings after valuable metals are extracted by secondary smelting of the copper slag can be fully utilized, and the discarding is reduced; the aggregate of the tailings obtained by the slow cooling mode is harder, and the granularity of the aggregate is limited in the range, so that the strength and durability of the permeable material are greatly improved, and the product quality is improved; meanwhile, the residual heavy metal elements in the tailings obtained by the treatment method have good stability, and the solid slag is effectively prevented from generating heavy metal pollution under the long-term rainwater immersion condition, so that the environmental protection performance of the baking-free permeable material can be improved. On the basis, the manufacturing method has the advantages of high utilization rate of tailings, high water permeable strength of the water permeable material, high wear resistance, good environmental protection performance, low cost and the like.

Aggregate with the particle size of 2.4-10 mm can be obtained through the primary screening process, solid slag with the particle size larger than the particle size is returned to be crushed and screened again, and slag powder with the particle size smaller than the particle size is sold or used as artificial fine sand. In a preferred embodiment, the manufacturing method further comprises: carrying out second screening treatment on the aggregate to obtain fine aggregate and coarse aggregate, wherein the granularity of the fine aggregate is 2.4-4.75 mm, and the granularity of the coarse aggregate is 4.76-10 mm; mixing fine aggregate and/or coarse aggregate, the cementing material and water, and then sequentially carrying out injection molding, demolding and curing treatment to obtain the baking-free water-permeable material. And the aggregates are subjected to secondary screening treatment to obtain fine aggregates and coarse aggregates with specific granularity, so that the preparation of the baking-free water-permeable material with different strengths and wear resistances is facilitated. In a preferred embodiment, when the aggregate is a fine aggregate, the weight ratio of the fine aggregate, the cementing material and the water is (22-32): (6-12): (2-8); in another preferred embodiment, when the aggregate is coarse aggregate, the weight ratio of the coarse aggregate, the cementing material and the water is (20-36): (4-15): (2-10); in another preferred embodiment, when the aggregate is a mixture of fine aggregate and coarse aggregate, the weight ratio of the coarse aggregate, the fine aggregate, the cementing material and the water is (14-22): (8-18): (10-20): (2-10). Limiting the proportion of the raw materials within the above range is beneficial to further improving the water permeability, strength and wear resistance of the permeable material.

In the above manufacturing method, the gelling material can be selected from gelling materials commonly used in the art. In a preferred embodiment, the cementitious material includes, but is not limited to, one or more of the group consisting of portland cement, ordinary portland cement, portland slag cement, pozzolanic portland cement, portland fly ash cement, and composite portland cement. The common cement-based cementing material is adopted, so that the permeable material does not need to be heated in the process of injection molding and consolidation, and belongs to a non-fired building material, thereby being beneficial to reducing the process cost, shortening the process flow and improving the product competitiveness. In the above-mentioned manufacturing method of cement with 42.5 grade or above according to the strength requirement of the permeable material, the injection molding process, the demolding process and the curing process can be performed by the conventional method in the art.

In a preferred embodiment, the injection molding process comprises: and fully and uniformly stirring the preparation raw materials of the baking-free water-permeable material, injecting the mixture into a plastic mould, vibrating the mixture on a vibration platform for 10-30 s to fully fill the cavity of the mould with the mixture, and troweling the molding surface. The injection molding vibration molding process is adopted, and because of poor fluidity, a rubber hammer or manual trowelling can be used, but the force is not too large, so that the aggregates are prevented from being broken to block the water seepage pores. More preferably, after the mixture is subjected to injection molding, covering a layer of plastic film on the surface of the brick, standing at room temperature or natural temperature for 24 hours to enable the green brick to form certain strength, and then demolding to obtain a green brick; and finally, curing the green bricks, and preparing the water permeable material after the green bricks reach a certain curing age.

In a preferred embodiment, the curing process includes, but is not limited to, natural water spray curing, steam curing, or autoclave curing;

preferably, the time of natural water spraying maintenance is more than or equal to 28 days; the steam curing time is 24-72 h; the temperature of the steam pressure curing is 150-180 ℃, and the steam pressure time is 10-24 h.

In order to improve the aesthetic property of the water permeable material, in a preferred embodiment, the manufacturing method further comprises: adding a water reducing agent and an optional pigment in the mixing process of the aggregate, the cementing material and the water. The pigment is preferably an iron oxide pigment, and more preferably red iron oxide, blue iron oxide, yellow iron oxide, or black iron oxide. In a preferred embodiment, the pigment is used in an amount of 2-8% by weight of the cementitious material.

In addition, the permeable material can be colored by adopting an integral coloring method, namely, pigment is directly added into the ingredients, and the mixture is uniformly mixed and then integrally molded; or a surface layer coloring method can be adopted, namely, the mixture added with the pigment is firstly put into a mould, the vibration is carried out, the thickness is 5-20 mm, then the mixture with the primary color is put into the residual space in the mould, and the vibration and the trowelling forming surface are carried out, so that the layer with the color is used as the surface layer of the brick.

The tailings obtained by the treatment method have the advantages of good wear resistance and strength, good environmental protection performance, low preparation cost, simple process and the like, so that the permeable material prepared from the tailings has the advantages of low cost, simple process, high environmental protection performance, short manufacturing period and the like. Meanwhile, when the permeable material is prepared by adopting the preparation method, the tailings after valuable metals are extracted by copper slag secondary smelting can be fully utilized, and the discarding is reduced; the aggregate of the tailings obtained by the slow cooling mode is harder, and the granularity of the aggregate is limited in the range, so that the strength and the wear resistance of the permeable material are greatly improved, and the product quality is improved; meanwhile, the residual heavy metal elements in the tailings obtained by the treatment method have good stability, and the solid slag is effectively inhibited from generating heavy metal pollution under the long-term rainwater immersion condition, so that the environmental protection performance of the baking-free permeable material can be improved. On the basis, the permeable material prepared by the manufacturing method has the advantages of high utilization rate of tailings, high permeable strength, high wear resistance, good environmental protection performance, low cost and the like.

The permeable material can be permeable bricks, and can also be directly poured into permeable concrete according to the size of a mould of a use site. After the water-permeable concrete is naturally cured for at least 28 days by film-covering and water-spraying, the permeable concrete is obtained, and compared with the preparation of permeable bricks, the preparation period of the permeable concrete is shorter and the efficiency is higher.

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.

The manufacturing process of the water permeable material in the example is shown in figure 1.

Reducing the copper slag at 1380-1450 ℃ to obtain copper slag tailings, wherein the copper slag tailings comprise the following components in percentage by weight: SiO 2₂38％，CaO 43％，Al₂O₃9%, MgO 6%, Fe 0.8% and impurities.

Example 1

Pouring copper slag tailings (with the temperature of 1420 ℃) into a slag pit, covering and insulating for 12 hours to cool the copper slag tailings to 800 ℃, wherein the cooling rate is 20 ℃/min between 650 ℃ and 1100 ℃.

And then, digging out copper slag tailings by using a bucket excavator, crushing, and screening to obtain tailings with the particle size of 3-4.75 mm, and storing the tailings as fine aggregates for later use.

Pouring 42.5-grade ordinary portland cement and water into a concrete mixer, stirring for 2min, adding the fine aggregate into the mixer after uniform slurry is formed, stirring for 3min, and adding a certain amount of water reducing agent according to the fluidity of the mixture during the stirring, and continuously stirring for 1-2 min. The total ingredients comprise the following aggregate in parts by weight: cement: water-12: 4: 1.

After the mixture is stirred uniformly, the mixture is poured into a container with the size of 200 × 100 × 60mm and the oil film brushed inside the container³And then placing the mould on a vibration platform to vibrate for 20s, then leveling the forming surface, covering the mould by using plastic cloth, standing for 1d indoors, and then demoulding to obtain a green brick. And putting the green bricks into a standard curing room with the temperature of 25 ℃ and the humidity of 95 percent, and curing for 28 days to obtain the pervious concrete bricks.

Example 2

Pouring the copper slag tailings (the temperature is 1380 ℃) subjected to secondary smelting into a slag ladle, naturally cooling for 24 hours, and cooling to 760 ℃, wherein the cooling rate between 650 ℃ and 1100 ℃ is 12 ℃/min.

And then, crushing the copper slag tailings, and storing the sieved tailings aggregates with the particle size of 5-10 mm for later use.

Pouring slag cement of 42.5 grades, water and iron oxide red into a concrete mixer, stirring for 2min, adding coarse aggregate into the mixer after uniform slurry is formed, stirring for 3min, and adding a certain amount of water reducing agent according to the fluidity of the mixture during stirring for continuously stirring for 1-2 min. The total ingredients comprise the following aggregate in parts by weight: cement: water: iron oxide red-20: 5:1: 0.05.

After the mixture is stirred uniformly, the mixture is poured into a container with the size of 200 × 100 × 60mm and the oil film brushed inside the container³And then placing the mould on a vibration platform to vibrate for 20s, then leveling the forming surface, covering the mould by using plastic cloth, standing for 1d indoors, and then demoulding to obtain a green brick. And (3) putting the green bricks into a steam curing chamber, performing steam curing for 24 hours, taking out the green bricks, and curing for 7 days in a natural environment after stacking to obtain the red through body permeable concrete brick.

Example 3

Pouring the copper slag tailings (the temperature is 1490 ℃) subjected to secondary smelting into a slag basin, naturally cooling for 15 hours, and then cooling to 820 ℃, wherein the cooling rate is 25 ℃/min between 650 ℃ and 1100 ℃.

And then crushing and screening the copper slag tailings to obtain fine aggregate with the particle size of 2.4-4.75 mm and coarse aggregate with the particle size of 4.76-10 mm, and respectively storing for later use.

Pouring the 42.5-grade composite Portland cement, water and iron oxide yellow into a concrete mixer, stirring for 2min, adding fine aggregate into the mixer after uniform slurry is formed, stirring for 3min, adding a water reducing agent according to the fluidity of the mixture, and continuously stirring for 1-2 min to obtain a yellow mixture. The total ingredients comprise the following aggregate in parts by weight: cement: water: iron oxide yellow is 16:5:1: 0.07.

And pouring the composite Portland cement of 42.5 grades and water into a concrete mixer, stirring for 2min, adding the coarse aggregate into the mixer after uniform slurry is formed, stirring for 3min, and adding a certain amount of water reducing agent into the mixer according to the fluidity of the mixture during the stirring, and continuously stirring for 1-2 min to prepare the primary-color mixture. The total ingredients comprise the following coarse aggregate in parts by weight: cement: water 18:6: 1.2.

After the yellow mixture is stirred uniformly, the mixture is poured into a container with the size of 200 × 100 × 60mm and the oil film brushed inside the container³The plastic mold of (1) was vibrated on the vibration table for 10 seconds. Then, pouring the primary color mixture into the mold, vibrating on a vibration platform for 20s, and then leveling the molding surface. During injection molding, the thickness ratio of the mixture of coarse aggregate and fine aggregate in the mold is controlled to be 1 (3-4).

Covering the mold with plastic cloth, standing for 1d indoors, and demolding to obtain green bricks. And stacking the green bricks in a natural environment, covering with a plastic film, maintaining for more than 28 days, continuously spraying water to the piled bricks during the maintenance, and then covering with a film. And curing for 28 days to obtain the composite permeable brick with the colored surface layer.

Example 4

The differences from example 1 are: the cooling rate is 50 ℃/min between 650 ℃ and 1100 ℃.

Example 5

The differences from example 1 are: the cooling rate is 10 ℃/min between 650 ℃ and 1100 ℃.

Example 6

The differences from example 1 are: the cooling rate is 25 ℃/min between 650 ℃ and 1100 ℃.

Example 7

The differences from example 1 are: the weight ratio of the fine aggregate to the cementing material to the water is 22: 12: 2.

example 8

The differences from example 1 are: the weight ratio of the fine aggregate to the cementing material to the water is 32: 6: 8.

example 9

The differences from example 2 are: the weight ratio of the aggregate, the cementing material, the water and the iron oxide red is 20: 4: 2: 0.05.

example 10

The differences from example 2 are: the weight ratio of the aggregate to the cementing material to the water is 36: 15: 10: 0.05.

comparative example 1

The differences from example 1 are: the cooling rate is 60 ℃/min between 650 ℃ and 1100 ℃.

The performance of the water permeable bricks prepared in examples 1 to 10 and comparative example 1 was tested, and the performance test method is shown in GB/T25993-2010 water permeable pavement brick and water permeable pavement slab. The test results are shown in Table 1.

TABLE 1

Examples	Splitting tensile strength (MPa)	Permeability coefficient × 100(cm/s)
			1	4.2	2.52
2	5.3	2.86
			3	3.6	2.42
4	3.1	2.2
			5	4.3	2.54
6	4.2	2.61
			7	5.5	2.80
8	5.2	2.91
			9	4.62	2.72
10	4.83	2.91
			Comparative example 1	2.1	1.97

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: compared with a comparative example, the material prepared by the method provided by the application has more excellent mechanical property and water permeability.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The treatment method of the copper slag is characterized by comprising the following steps:

carrying out reduction smelting on the copper slag to obtain valuable metal and reduction slag;

cooling the slag to be less than or equal to 500 ℃ to obtain tailings, wherein the cooling rate of the tailings at 650-1100 ℃ is less than or equal to 50 ℃/min.

2. The treatment method according to claim 1, wherein the cooling rate of the tailings at 650-1100 ℃ is 10-25 ℃/min during the cooling process.

3. The method according to claim 1 or 2, wherein the temperature of the reduction smelting is 1350-1500 ℃.

4. A manufacturing method of a baking-free water-permeable material is characterized by comprising the following steps:

crushing and primary screening treatment are carried out on the tailings obtained by the treatment method of any one of claims 1 to 3 to obtain aggregate, wherein the granularity of the aggregate is 2.4-10 mm;

and mixing the aggregate, the cementing material and water, and sequentially carrying out injection molding, demolding and curing treatment to obtain the baking-free water-permeable material.

5. The manufacturing method according to claim 4, characterized by further comprising:

performing second screening treatment on the aggregate to obtain fine aggregate and coarse aggregate, wherein the granularity of the fine aggregate is 2.4-4.75 mm, and the granularity of the coarse aggregate is 4.76-10 mm;

and mixing the fine aggregate and/or the coarse aggregate, the cementing material and the water, and then sequentially carrying out the injection molding, the demolding and the maintenance treatment to obtain the baking-free permeable material.

6. The manufacturing method according to claim 5, wherein when the aggregate is the fine aggregate, the weight ratio of the fine aggregate, the binding material, and the water is (22-32): (6-12): (2-8);

when the aggregate is the coarse aggregate, the weight ratio of the coarse aggregate, the cementing material and the water is (20-36): (4-15): (2-10);

when the aggregate is a mixture of the fine aggregate and the coarse aggregate, the weight ratio of the coarse aggregate to the fine aggregate to the cementing material to the water is (14-22) to (8-18) to (10-20) to (2-10).

7. The manufacturing method according to any one of claims 4 to 6, wherein the cementitious material is selected from one or more of the group consisting of portland cement, ordinary portland cement, portland slag cement, pozzolanic portland cement, fly ash portland cement, and composite portland cement.

8. The manufacturing method according to any one of claims 4 to 6, wherein the curing process is selected from natural water spray curing, steam curing, or autoclave curing;

preferably, the time of the natural water spraying maintenance is more than or equal to 28 days;

the steam curing time is 24-72 h;

the steam-pressure curing temperature is 150-180 ℃, and the steam-pressure time is 10-24 h.

9. The manufacturing method according to claim 8, characterized by further comprising: adding a water reducing agent and an optional pigment in the mixing process of the aggregate, the cementing material and the water;

preferably, the pigment is an iron oxide based pigment, more preferably red, blue, yellow or black iron oxide.

10. The manufacturing method according to claim 9, wherein the pigment is used in an amount of 2 to 8% by weight based on the weight of the cement.

11. A baking-free water-permeable material, characterized in that the raw materials for preparing the baking-free water-permeable material comprise tailings obtained by the processing method of any one of claims 1 to 3, and/or the baking-free water-permeable material is prepared by the manufacturing method of any one of claims 4 to 10.