CN114014574B - Treatment method of high-sulfur copper tailing slag and concrete prepared from modified copper tailings - Google Patents

Treatment method of high-sulfur copper tailing slag and concrete prepared from modified copper tailings Download PDF

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CN114014574B
CN114014574B CN202111413224.1A CN202111413224A CN114014574B CN 114014574 B CN114014574 B CN 114014574B CN 202111413224 A CN202111413224 A CN 202111413224A CN 114014574 B CN114014574 B CN 114014574B
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parts
slag
copper tailing
tailing slag
sulfur
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CN114014574A (en
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包明
郑涛
王军
赵日煦
高飞
熊龙
李兴
邢菊香
黄灿
余昆
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China West Construction Group Co Ltd
China Construction Ready Mixed Concrete Co Ltd
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China West Construction Group Co Ltd
China Construction Ready Mixed Concrete Co Ltd
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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
    • 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
    • C04B20/02—Treatment
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/12—Waste materials; Refuse from quarries, mining or the like
    • 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
    • C04B20/02—Treatment
    • C04B20/023—Chemical treatment
    • 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
    • C04B20/02—Treatment
    • C04B20/04—Heat treatment
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2111/20—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical Kinetics & Catalysis (AREA)
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  • Mining & Mineral Resources (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

The invention discloses a method for treating high-sulfur copper tailing slag, which comprises the following steps: 1) Pre-treating; carrying out magnetic separation on the high-sulfur copper tailing slag, and then adding water to obtain copper tailing slag dispersion liquid; 2) Chemical modification; adding a modifier into the obtained copper tailing slag dispersion liquid, and uniformly stirring; 3) And (3) heat treatment: oxidizing in oxygen atmosphere at 60-90 deg.c, classifying in cyclone, selecting 200 mesh or higher grain material, and dewatering to obtain the modified copper tailing slag. The obtained modified copper tailing slag is applied to preparing concrete, so that the shrinkage cracks and internal pores of the concrete can be effectively reduced, the problem of later strength shrinkage of the concrete is solved, and good working performance and durability are considered; is suitable for popularization and application.

Description

Treatment method of high-sulfur copper tailing slag and concrete prepared from obtained modified copper tailings
Technical Field
The invention belongs to the field of constructional engineering, and particularly relates to a high-sulfur copper tailing slag treatment method and concrete prepared from the obtained modified copper tailings.
Background
Copper tailings are generally directly discharged into a tailing pond in a slurry form for stockpiling, the large stockpiling of the copper tailings not only occupies land resources and consumes manpower and material resources for management, but also contains a large amount of harmful substances which seriously affect peripheral underground water resources and ecological environment. Therefore, how to realize the recycling of the copper tailings and improve the comprehensive utilization rate is not slow. At present, china makes some progress in the aspect of development and utilization of copper tailings, but the comprehensive utilization rate is low, and the problem cannot be solved fundamentally. The copper tailing slag is used as fine aggregate in concrete, so that the shortage pressure of natural sand can be relieved, the comprehensive utilization rate of the copper tailing can be improved, and the environmental pollution is reduced.
However, due to the limitations of a series of factors such as the technical level, equipment performance, economic conditions, manual operation of actual production and the like in the past and the current industries, the beneficiation process of copper ores is not complete enough, so that valuable elements cannot be avoided to remain in tailings, the tailings cannot be extracted completely, according to data investigation, the average iron content of the tailings in China is 11% and can reach 27% at most, and the same amount of huge iron metal remains in the copper tailings. Copper ores are often associated with sulfur, e.g. to form CuS, feS 2 And after copper and sulfur selecting treatment, the sulfur content of the obtained copper tailings is still high. Particularly, residual sulfate ions in copper ore treated by sulfuric acid are left in copper tailings, and the sulfate ions are generated from sulfur minerals in the copper tailings under the action of air and water, so that delayed ettringite and merwinite are potentially harmful when the sulfate is excessive. GB/T14684 in the national standard stipulates that the content of sulfide and sulfate in the construction sand cannot exceed 0.5wt%, so in order to realize the application of high-sulfur copper tailings as fine aggregates in concrete, the problem of excessive sulfide and sulfate in the copper tailings must be solved.
Disclosure of Invention
The invention aims to solve the problems of environmental pollution and resource waste caused by accumulation of high-sulfur copper tailing slag, incapability of effectively applying the high-sulfur copper tailing slag in concrete and the like, and provides a method for treating the high-sulfur copper tailing slag.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for treating high-sulfur copper tailing slag comprises the following steps:
1) Pre-treating; carrying out magnetic separation on the high-sulfur copper tailing slag, and preliminarily separating valuable substances containing magnetism; then adding water to obtain copper tailing slag dispersion liquid;
2) Chemical modification; adding a modifier into the obtained copper tailing slag dispersion liquid, and uniformly stirring;
3) And (3) heat treatment: oxidizing in oxygen atmosphere at 60-90 deg.c, classifying in cyclone, selecting 200 mesh or higher grain material, and dewatering to obtain the modified copper tailing slag.
In the above scheme, the main chemical compositions and contents of the high-sulfur copper tailings include: sulfur content (in SO) 3 Calculated) 1.0 to 8.0wt% of Fe 2 O 3 10-25 wt%, caO 15-40 wt%, siO 2 10-30 wt%, wherein the grain diameter of 200 meshes is more than or equal to 40wt%, and the water content is less than or equal to 20wt%.
In the scheme, the magnetic field intensity adopted in the magnetic separation step is 1.4-1.8T.
In the scheme, the water adding amount in the step 1) is 1-3 times of the mass of the high-sulfur copper tailing slag.
In the scheme, the modifier is formed by compounding 6-9 parts of carbide slag and 1-4 parts of steel slag powder.
In the scheme, the oxidation treatment time is 0.5-1 h.
In the scheme, the content of calcium oxide in the carbide slag is 50-75 wt%; the surface area of the steel slag powder is more than 450m 2 /kg。
In the scheme, the mass ratio of the copper tailing slag dispersion liquid introduced in the step 2) to the modifier is (3-10) 100.
The concrete prepared from the modified copper tailings comprises the following components in parts by weight: 60-120 parts of cement clinker, 80-180 parts of steel slag powder, 80-300 parts of slag powder, 20-40 parts of metakaolin, 160-175 parts of water, 400-600 parts of modified copper tailing slag, 200-560 parts of coarse sand, 950-1150 parts of coarse aggregate and 8-12 parts of polycarboxylic acid water reducer.
In the above scheme, the cement clinker is silicate cement clinker, wherein C 3 The content of A is less than or equal to 8wt percent.
In the scheme, the specific surface area of the steel slag powder is more than or equal to 450m 2 The activity index of/kg, 28d is more than or equal to 80 percent.
In the scheme, the slag powder is S95 granulated blast furnace slag powder, and the 28d activity index is more than or equal to 95%.
In the above scheme, siO in the metakaolin 2 With Al 2 O 3 The sum of the mass percentage content of the components is more than or equal to 50wt percent, and the specific surface area is more than or equal to 2300m 2 /kg。
In the scheme, the coarse sand comprises one or two of natural sand and machine-made sand, the fineness modulus is 2.3-3.9, and the content of stone powder is less than or equal to 3wt%; the coarse aggregate is crushed stone with continuous gradation of 5-25 mm.
The principle of the invention is as follows:
aiming at the problems that the high-sulfur copper tailings in the prior art cannot be directly used in the existing concrete system and the like, the invention utilizes a physical and chemical method to convert the sulfur element in the high-sulfur copper tailings, reduces the potential hazards of delayed ettringite and mersosite: firstly removing magnetic substances in high-sulfur copper tailings under a magnetic condition, and then absorbing SO in ore dressing in the tailings by using a composite modifier 4 2- And CuS, feS 2 Oxidation of isosulfides to form CaSO 4 (ii) a Gypsum in the modified copper tailing slag is used as retarder and excitant of a gelling system, residual carbide slag and Ca (OH) 2 As an excitant of a low-cement clinker system, tailings are used as concrete sand for preparing high-sulfur copper tailing-based concrete; ca (OH) 2 During hydration asThe excitant has hydration reaction with steel slag, slag and metakaolin, ca (OH) 2 The calcium hydroxide is gradually consumed, main hydration products such as CSH gel, feldspar and zeolite with similar structures are finally formed, and the hydration products such as calcium hydroxide and hydrated calcium aluminate which are easy to be corroded by sulfate do not exist basically, so that the internal pore structure of the material is effectively improved, and the internal sulfate corrosion resistance is enhanced.
Compared with the prior art, the invention has the beneficial effects that:
1) The method for treating the high-sulfur copper tailing slag can relieve the environmental pollution caused by tailing storage and accumulation, and reduce resource waste and environmental pollution; the obtained modified copper tailing slag can partially replace natural sand, so that the technical problems of insufficient natural sand resources and the like are solved; meanwhile, the electroslag and the steel slag adopted for modification are solid wastes, so that the method has remarkable economic and social benefits;
2) The method for treating the high-sulfur copper tailing slag is simple, low in cost, strong in practicability and large in market demand, and is beneficial to standardized production and popularization;
3) The modified copper tailing slag can remarkably improve the problems of overhigh expansion rate, obvious reduction of later strength and the like caused by introducing high-sulfur copper tailing slag into a concrete system, effectively reduce the shrinkage cracks and internal pores of concrete, and solve the problems of later strength shrinkage and the like of the concrete; meanwhile, the obtained concrete has good workability, good fluidity, no bleeding and good durability.
Detailed Description
The following examples further illustrate the invention in order that it may be better understood. However, the present invention is not limited to the following examples.
In the following examples, the cement clinker used was portland cement clinker, C in which 3 The content of A is 6.6wt%;
the coarse sand is machine-made sand, the fineness modulus is 3.6, and the content of stone powder is 2.1wt%;
the coarse aggregate is crushed stone with continuous gradation of 5-25 mm;
the specific surface area of the steel slag powder is 460m 2 Kg,28d activity index 85%;
the slag powder is S95 granulated blast furnace slag powder, and the activity index is 96% at 28 d;
SiO in metakaolin 2 With Al 2 O 3 The sum of the mass percent of the components is 63wt percent, and the specific surface area is 2800m 2 /kg。
In the following examples, the chemical composition of the high-sulfur copper tailings was obtained using X-ray fluorescence analysis (XRF).
Example 1
A method for treating high-sulfur copper tailing slag comprises the following steps:
1) The adopted high-sulfur copper tailing slag mainly comprises the following chemical components in percentage by weight: SO (SO) 3 4.5wt％，Fe 2 O 3 23.1wt％，CaO 35.1wt％，SiO 2 20.1wt%, 70wt% of particles with the particle size of more than 200 meshes and 12wt% of water content, separating the high-sulfur copper tailing slag in a 1.4T magnetic environment, and adding 1 time of water by mass to obtain copper tailing slag dispersion;
2) Adding 6 parts of modifier into 100 parts of the obtained copper tailing slag dispersion liquid, adding into a stirring tank, and stirring for 3min; wherein the added modifier is formed by compounding carbide slag and steel slag powder according to the mass ratio of 7:3, and the calcium oxide content of the carbide slag is 70wt%;
3) Oxidizing the product obtained in the step 2) for 0.5h at 80 ℃ in an oxygen atmosphere, classifying by a cyclone, selecting granules with the granularity of more than 200 meshes, and dehydrating to obtain the treated desulfurization modified copper tailing slag.
Application example
The obtained desulfurization modified copper tailing slag is applied to preparing concrete, and the components and the parts by weight are as follows: 70 parts of cement clinker, 120 parts of steel slag powder, 150 parts of slag powder, 20 parts of metakaolin, 600 parts of modified copper tailing slag, 300 parts of coarse sand, 980 parts of coarse aggregate, 165 parts of water and 8 parts of polycarboxylic acid water reducer.
Example 2
A method for treating high-sulfur copper tailing slag comprises the following steps:
1) The adopted high-sulfur copper tailing slag mainly comprises the following chemical components in percentage by weight: SO 3 6.3wt％，Fe 2 O 3 18.0wt％，CaO 27.8wt％，SiO 2 19.8wt%, 76wt% of particles with the particle size of more than 200 meshes and 13wt% of water content, separating the high-sulfur copper tailing slag in a 1.6T magnetic environment, and adding 2 times of water by mass to obtain copper tailing slag dispersion liquid;
2) Adding 5 parts of modifier into 100 parts of the obtained copper tailing slag dispersion liquid, adding into a stirring tank, and stirring for 3min; the modifier added is formed by compounding carbide slag and steel slag powder according to the mass ratio of 8:2, and the calcium oxide content of the carbide slag is 76wt%;
3) Oxidizing the product obtained in the step 2) for 1h at 85 ℃ in an oxygen atmosphere, classifying by a cyclone, selecting granules with the granularity of more than 200 meshes, and dehydrating to obtain the treated desulfurization modified copper tailing slag.
Application example
The obtained desulfurization modified copper tailing slag is applied to preparing concrete, and the components and the parts by weight are as follows: 80 parts of cement clinker, 100 parts of steel slag powder, 200 parts of slag powder, 20 parts of metakaolin, 450 parts of modified copper tailing slag, 450 parts of coarse sand, 950 parts of coarse aggregate, 160 parts of water and 10 parts of polycarboxylic acid water reducing agent.
Example 3
A method for treating high-sulfur copper tailing slag comprises the following steps:
1) The adopted high-sulfur copper tailing slag mainly comprises the following chemical components in percentage by weight: SO (SO) 3 5.7wt％，Fe 2 O 3 18.0wt％，CaO 26.1wt％，SiO 2 28.4wt%, 70wt% of particles with the particle size of more than 200 meshes and 8wt% of water content, separating the high-sulfur copper tailing slag in a 1.8T magnetic environment, and adding 1 time of water by mass to obtain copper tailing slag dispersion liquid;
2) Adding 8 parts of modifier into 100 parts of the obtained copper tailing slag dispersion liquid, adding into a stirring tank, and stirring for 3min; wherein the added modifier is formed by compounding carbide slag and steel slag powder according to the mass ratio of 9:1, and the calcium oxide content of the carbide slag is 75wt%;
3) Oxidizing the product obtained in the step 2) for 1h at 90 ℃ in an oxygen atmosphere, classifying by a cyclone, selecting granules with the granularity of more than 200 meshes, and dehydrating to obtain the treated desulfurization modified copper tailing slag.
Application example
The obtained desulfurization modified copper tailing slag is applied to preparing concrete, and the components and the weight portions thereof are as follows: 120 parts of cement clinker, 150 parts of steel slag powder, 220 parts of slag powder, 20 parts of metakaolin, 400 parts of modified copper tailing slag, 500 parts of coarse sand, 1000 parts of coarse aggregate, 160 parts of water and 12 parts of polycarboxylic acid water reducer.
Comparative example 1
Comparative example 1 the concrete was prepared in substantially the same manner as in example 1, except that modified copper tailings were replaced with fine sand having a fineness modulus of 1.6; the concrete comprises the following components in proportion: 70 parts of cement clinker, 120 parts of steel slag powder, 150 parts of slag powder, 20 parts of metakaolin, 600 parts of fine sand, 300 parts of coarse sand, 980 parts of coarse aggregate, 165 parts of water and 8 parts of polycarboxylic acid water reducer.
Comparative example 2
Comparative example 2 the concrete was prepared in substantially the same manner as in example 2, except that: the adopted high-sulfur copper tailing slag is only subjected to cyclone classification, and granules with more than 200 meshes are selected for preparing concrete; the concrete mixing proportion is as follows: 80 parts of cement clinker, 100 parts of steel slag powder, 200 parts of slag powder, 20 parts of metakaolin, 450 parts of high-sulfur copper tailing slag, 450 parts of coarse sand, 950 parts of coarse aggregate, 160 parts of water and 10 parts of polycarboxylic acid water reducer.
Comparative example 3
The concrete of comparative example 1 was prepared in substantially the same manner as example 3, except that: in the treatment process of the high-sulfur copper tailing slag, the oxidation treatment step in the step 3) is not carried out; the concrete mixing proportion is as follows: 120 parts of cement clinker, 150 parts of steel slag powder, 220 parts of slag powder, 20 parts of metakaolin, 400 parts of modified copper tailing slag, 500 parts of coarse sand, 900 parts of coarse aggregate, 160 parts of water and 12 parts of polycarboxylic acid water reducer.
The concrete described in examples 1 to 3 and comparative examples 1 to 3 were subjected to respective tests for workability, mechanical properties, etc., and the results are shown in Table 1.
TABLE 1 results of performance test of concrete obtained in examples 1 to 3 and comparative examples 1 to 3
Figure BDA0003375066320000051
The results show that when the desulfurization modified copper tailing slag sand is used for preparing concrete, the setting time is normal, the internal pores are greatly reduced, the 90d strength is not reduced, and meanwhile, the workability, the fluidity and the durability of the concrete are good. However, in comparative example 1, the common fine sand is used to replace the modified copper tailing slag to prepare the concrete, the activity of the sulphoaluminate and alkali-activated steel slag and slag powder in the modified copper tailing slag is not generated, the setting time is delayed, and the strength is slowly developed.
In comparative example 2, no alkali-activating effect was exhibited by the copper tailings alone without modification, so that the strength developed slowly. Comparative example 3 copper tailings slag contains partial sulphoaluminate and most sulphide, without high temperature treatment, sulphide cannot be converted into sulphoaluminate, only alkali excitation effect exists but gypsum amount is insufficient, so that setting time is abnormal and strength develops slowly.
Comparative examples 5 to 7
The formulation of the concrete in comparative examples 5 to 7 is shown in table 2, wherein the cement is P · O42.5 cement, the fly ash is class I fly ash, the slag powder is S95 slag powder, the sand is common river sand, the fineness modulus is 2.8, and the stone is 5 to 25 continuous graded crushed stone; the additive is a polycarboxylic acid high-performance water reducing agent.
TABLE 2 C30, C40, C50 general concrete mix ratio (kg/m) 3 )
Numbering Cement Fly ash Slag powder Sand Stone (stone) Water (W) Additive agent
Comparative example 5 200 100 40 900 1080 165 8
Comparative example 6 250 90 60 900 980 160 12
Comparative example 7 330 60 70 850 950 160 12
The concrete obtained in examples 1 to 3 and comparative examples 5 to 7 were subjected to durability tests, respectively, and the results are shown in Table 3; the test of the sulfuric acid corrosion resistance of the concrete refers to the standard GB/T50082 Experimental method for the long-term performance and durability of common concrete, and the concrete is subjected to drying shrinkage cycle test 150 times in a 5% sodium sulfate solution.
TABLE 3 test results of sulfuric acid etching resistance of the concretes obtained in examples 1 to 3 and comparative examples 5 to 7
Figure BDA0003375066320000061
It can be seen from table 3 that the concrete prepared by using the desulfurized modified copper tailing slag sand has good sulfuric acid corrosion resistance compared with a common concrete system.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims (7)

1. A method for treating high-sulfur copper tailing slag is characterized by comprising the following steps:
1) Pre-treating; carrying out magnetic separation on the high-sulfur copper tailing slag, and then adding water to obtain copper tailing slag dispersion liquid;
2) Chemical modification; adding a modifier into the obtained copper tailing slag dispersion liquid, and uniformly stirring;
3) And (3) heat treatment: carrying out oxidation treatment in an oxygen atmosphere at the temperature of 60-90 ℃, then classifying by a cyclone, selecting granules with a screen of more than 200 meshes, and dehydrating to obtain treated modified copper tailing slag;
the modifier is formed by compounding 6~9 parts of carbide slag and 1~4 parts of steel slag powder;
the water adding amount in the step 1) is 1~3 times of the mass of the high-sulfur copper tailing slag;
the mass ratio of the copper tailing slag dispersion liquid introduced in the step 2) to the modifier is 100 (3-10).
2. The method of claim 1, wherein the high-sulfur copper tailings have a major chemical composition and content comprising: SO (SO) 3 1.0~8.0wt%，Fe 2 O 3 10~25wt%，CaO 15~40wt%，SiO 2 10 to 30wt%; wherein the grain diameter of 200 meshes is more than or equal to 40wt%, and the water content is less than or equal to 20wt%.
3. The method for treating high-sulfur copper tailings slag according to claim 1, wherein the magnetic field strength adopted in the magnetic separation step is 1.4 to 1.8T.
4. The method for treating high-sulfur copper tailing slag according to claim 1, wherein the oxidation treatment time is 0.5 to 1h.
5. The method for treating high-sulfur copper tailing slag according to claim 1, wherein the content of calcium oxide in the carbide slag is 50 to 75wt%; the surface area of the steel slag powder is more than 450m 2 /kg。
6. Concrete prepared from the modified copper tailings of 1~5 of any of claims, wherein the concrete comprises the following components in parts by weight: 60-120 parts of cement clinker, 80-180 parts of steel slag powder, 80-300 parts of slag powder, 20-40 parts of metakaolin, 160-175 parts of water, 400-600 parts of modified copper tailing slag, 200-560 parts of coarse sand, 950-1150 parts of coarse aggregate and 8-12 parts of polycarboxylic acid water reducer.
7. The concrete according to claim 6, wherein the coarse sand comprises one or two of natural sand and machine-made sand, the fineness modulus is 2.3 to 3.9, and the content of stone powder is less than or equal to 3wt%; the coarse aggregate is broken stone with continuous gradation of 5-25mm.
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