CN113773026B - Zinc-containing solid waste-based mine cemented filling material and preparation method thereof - Google Patents
Zinc-containing solid waste-based mine cemented filling material and preparation method thereof Download PDFInfo
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- CN113773026B CN113773026B CN202111181020.XA CN202111181020A CN113773026B CN 113773026 B CN113773026 B CN 113773026B CN 202111181020 A CN202111181020 A CN 202111181020A CN 113773026 B CN113773026 B CN 113773026B
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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
- 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
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C04B24/085—Higher fatty acids
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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
- 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
- C04B28/08—Slag cements
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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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/17—Mixtures thereof with other inorganic cementitious materials or other activators with calcium oxide containing activators
- C04B7/19—Portland cements
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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
- 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
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a mine cemented filling material based on zinc-containing solid waste and a preparation method thereof, belonging to the technical field of harmless treatment of solid waste. The mine cemented filling material based on zinc-containing solid waste comprises the following raw materials in parts by weight: 100 to 150 portions of Portland cement, 100 to 120 portions of zinc-containing solid waste, 1500 to 1800 portions of aggregate, 40 to 50 portions of soluble stearate, 10 to 20 portions of water reducing agent and 400 to 450 portions of water. The mine cemented filling material based on the zinc-containing solid waste provided by the invention has high strength and strong zinc fixation performance after being hydrated and hardened, and provides a safe and effective harmless treatment method for the treatment of the zinc-containing solid waste.
Description
Technical Field
The invention relates to the technical field of harmless treatment of solid wastes, in particular to a mine cemented filling material based on zinc-containing solid wastes and a preparation method thereof.
Background
The cementing filling material is generally prepared by taking broken stones, river sand or gobi aggregate or tailing sand as aggregate, mixing the aggregate with cementing agents such as cement and the like by adding water, stirring to form slurry or paste, and conveying the slurry or paste to a filling area in a pipeline pumping or gravity self-flowing mode. The cemented filling material contains a certain proportion of cementing agent, has higher strength and integrity and higher operation safety, and can improve the recovery rate of ores and the operation efficiency of a stope while meeting various underground supporting requirements. Along with the popularization and application of mine filling mining technology, the cementing agent for filling is continuously updated, and an effective way is provided for resource utilization of bulk industrial solid wastes.
The steel industry is a very important basic industry, a large amount of solid waste is inevitably generated in the production process of the steel industry, the generation amount of the solid waste is generally 8% -12% of the steel yield, the solid waste comprises huge amount of steel dust, and how to treat the huge amount of the steel dust becomes an important subject of the steel industry. The dust of the steel plant divides the solid waste into iron-containing solid waste and zinc-containing solid waste according to the content of iron and zinc. Mainly blast furnace dust generated in the steel and iron process, the treatment difficulty is high, and the attention is paid to how to treat the zinc-containing solid waste in the steel and iron plant. The current treatment methods mainly comprise: the landfill method, the physical method, the wet method, the fire method, the plasma method and the like still face a lot of difficulties, and how to provide a safe and effective harmless treatment method is a technical problem to be solved urgently in the field.
Disclosure of Invention
Aiming at the technical problems, the invention provides a zinc-containing solid waste-based cemented filling material for mines and a preparation method thereof. The zinc-containing solid waste is used as a cementing agent of the cementing filling material to replace partial cement, so that the using amount of the cement is saved, free calcium hydroxide generated in the hydration process of the cementing filling material and added soluble stearate form calcium stearate, the generated calcium stearate has certain hydrophilicity, the exuded zinc can be fixed in the exudation process of the zinc-containing solid waste, the zinc stearate which is completely insoluble in water is generated, and the problem of treatment of the zinc-containing solid waste is solved.
In order to realize the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is as follows: the mine cemented filling material based on zinc-containing solid waste is provided, and comprises the following raw materials in parts by mass: 100 to 150 parts of Portland cement, 100 to 120 parts of zinc-containing solid waste, 1500 to 1800 parts of aggregate, 40 to 50 parts of soluble stearate, 10 to 20 parts of water reducing agent and 400 to 450 parts of water.
Preferably, the portland cement comprises one or more of ordinary portland cement, portland slag cement, portland pozzolan cement, portland fly ash cement, or composite portland cement.
Preferably, the zinc-containing solid waste comprises steelmaking blast furnace dust.
Preferably, the grain diameter of the zinc-containing solid waste is less than or equal to 0.1mm, and the content of CaO is 20-30%.
The content of active CaO in the zinc-containing solid waste is 20-30%, if the content of the active CaO is too low, the quantity of generated hydrates is small, and the strength of the prepared zinc-containing solid waste as a cementing filler is low; if the content of active CaO is too high, high-alkaline hydrated calcium silicate is generated, which is also not beneficial to ensuring the strength of the prepared zinc-containing solid waste as a cementing filling material.
Preferably, the aggregate comprises one or more of waste stone, tailings or coal gangue with the particle size of less than or equal to 5 mm.
The aggregate used in the invention is some waste solid materials in the process of mining, and when the aggregate is used for filling mines, the aggregate can be used as local materials, thus saving the transportation cost of the materials and solving the problem of solid waste accumulation.
Preferably, the soluble stearate comprises sodium stearate and/or potassium stearate.
The stearate is added, so that the effect of fixing zinc can be achieved, and the dosage of the water reducing agent can be reduced.
Preferably, the water reducing agent comprises one or more of lignosulphonate, naphthalene sulphonate or sulphamate.
The second technical scheme of the invention is as follows: the preparation method of the mine cemented filling material based on the zinc-containing solid waste comprises the following steps:
mixing portland cement, zinc-containing solid waste, coarse aggregate, fine aggregate and a water reducing agent to obtain a mixture A; mixing soluble stearate with water to obtain a mixture B; and (3) mixing the mixture A and the mixture B, and uniformly stirring to obtain the mine cemented filling material based on the zinc-containing solid wastes.
The beneficial technical effects of the invention are as follows:
the invention takes the zinc-containing solid waste as the cementing agent of the cementing filling material to replace part of cement, thereby saving the using amount of the cement, simultaneously, free calcium hydroxide generated in the hydration process of the cementing filling material and added soluble stearate form calcium stearate, the generated calcium stearate has certain hydrophilicity, the zinc which is exuded can be fixed in the exudation process of the zinc which is contained in the zinc-containing solid waste, and the zinc stearate which is completely insoluble in water is generated, thereby solving the treatment problem of the zinc-containing solid waste.
According to the invention, the soluble stearate is added and directionally adsorbed on the zinc-containing solid waste surface, so that the surface of the soluble stearate has negative charges, an electrostatic repulsion effect is formed, the soluble stearate is promoted to be mutually dispersed, a flocculation structure is disintegrated, and wrapped part of water is released to participate in flowing, so that the fluidity of the mine cemented filling material based on the zinc-containing solid waste is effectively increased, the compactness of the filling material can be effectively improved when the mine cemented filling material is used for mine filling, and the strength of the cured filling material is improved.
The mine cemented filling material based on zinc-containing solid waste provided by the invention has high strength after maintenance, strong zinc-fixing performance, and provides a safe and effective harmless treatment method for treating the zinc-containing solid waste.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The contents of the main components in the steelmaking blast furnace ash used in the embodiment of the invention are shown in the table.
TABLE 1
The contents of the main components in the steel-making blast furnace ash used in comparative example 2 of the present invention are shown in table 2.
TABLE 2
Example 1
Preparing a mine cemented filling material based on zinc-containing solid wastes:
weighing raw materials according to the proportion of 100 parts of 42.5 common Portland cement, 120 parts of steelmaking blast furnace ash with the particle size of less than or equal to 0.1mm, 1500 parts of waste stone with the particle size of less than or equal to 5mm, 40 parts of sodium stearate, 20 parts of sodium lignosulfonate and 400 parts of water;
mixing 42.5 ordinary portland cement, steelmaking blast furnace dust, broken stone, river sand and sodium lignosulfonate, and uniformly stirring to obtain a mixture A;
mixing sodium stearate with water, and uniformly stirring to obtain a mixture B;
and (3) mixing the mixture A and the mixture B again, and stirring for 15min to prepare the mine cemented filling material based on the zinc-containing solid wastes.
Example 2
Preparing a mine cemented filling material based on zinc-containing solid wastes:
weighing raw materials according to the proportion of 150 parts of 42.5 portland slag cement, 100 parts of steelmaking blast furnace dust with the particle size of less than or equal to 0.1mm, 1000 parts of waste rock with the particle size of less than or equal to 5mm, 800 parts of tailings with the particle size of less than or equal to 5mm, 50 parts of potassium stearate, 10 parts of magnesium lignosulfonate and 450 parts of water;
mixing 42.5 slag portland cement, steelmaking blast furnace dust, broken stones, river sand and magnesium lignosulfonate, and uniformly stirring to obtain a mixture A;
mixing potassium stearate with water, and uniformly stirring to obtain a mixture B;
and (3) mixing the mixture A and the mixture B again, and stirring for 15min to prepare the mine cemented filling material based on the zinc-containing solid wastes.
Example 3
Weighing raw materials according to the proportion of 120 parts of 42.5 fly ash Portland cement, 110 parts of steelmaking blast furnace ash with the particle size of less than or equal to 0.1mm, 1200 parts of tailings with the particle size of less than or equal to 5mm, 500 parts of coal gangue with the particle size of less than or equal to 5mm, 45 parts of sodium stearate, 10 parts of sodium lignosulfonate and 420 parts of water;
mixing 42.5 fly ash portland cement, steelmaking blast furnace dust, broken stone, river sand and sodium lignosulfonate, and uniformly stirring to obtain a mixture A;
mixing sodium stearate and water, and uniformly stirring to obtain a mixture B;
and (3) mixing the mixture A and the mixture B again, and stirring for 15min to prepare the mine cemented filling material based on the zinc-containing solid waste.
Comparative example 1
The addition of sodium stearate was omitted compared to example 1, and the other conditions were the same as in example 1.
Comparative example 2
The steelmaking blast furnace dust in example 1 was replaced with the steelmaking blast furnace dust having the composition shown in Table 2, as compared with example 1, and the other conditions were the same as in example 1.
Comparative example 3
The steel-making blast furnace ash was replaced with 42.5 portland cement of equal quality as compared with example 1, and the other conditions were the same as in example 1.
Compressive strength and zinc toxicity leaching determination:
injecting the zinc-containing solid waste-based mine cemented filling materials prepared in the examples 1-3 and the comparative examples 1-3 into a standard test mold of 70.7 multiplied by 70.7mm, and oscillating for 30s by using a vibration table; standing and maintaining for 24h, removing the mold, respectively placing into a standard maintenance box for maintenance, and respectively performing uniaxial unconfined compressive strength test and zinc toxicity leaching (determined according to HJ557-2009 solid waste leaching toxicity method horizontal oscillation method) test when the node reaches the age; the results of the uniaxial unconfined compressive strength measurements are shown in table 3; the results of the zinc toxicity leaching assay are shown in table 4.
TABLE 3
As can be seen from Table 3, the strength of the filler prepared by using the steelmaking blast furnace ash to replace part of cement as a cementing agent is slightly lower than that of the filler prepared by using all cement as a cementing agent, the difference is not great overall, and the steelmaking blast furnace ash can be used for partially replacing cement to prepare a cementing filler for mines. The compression resistance of the prepared filling material is reduced by adopting the steelmaking blast furnace dust with overhigh calcium oxide content. In the case of omitting the addition of sodium stearate, the compressive strength of the cured filler is directly affected due to the low fluidity of the prepared filler.
TABLE 4
Remarking: ND in Table 4 indicates that the zinc leaching concentration is less than 1 mg.L -1 The detection limit of the zinc leaching concentration is 0.01 mg.L -1 。
It can be seen from table 4 that, under the condition that stearate is not added, a large amount of zinc element is leached, and after stearate is added, the zinc leaching concentration of the hardened body is extremely low, which meets the limit requirement of the drinking water standard in China and can be ignored.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (3)
1. The mine cemented filling material based on zinc-containing solid wastes is characterized by comprising the following raw materials in parts by mass: 100 to 150 parts of Portland cement, 100 to 120 parts of zinc-containing solid waste, 1500 to 1800 parts of aggregate, 40 to 50 parts of soluble stearate, 10 to 20 parts of water reducing agent and 400 to 450 parts of water;
the soluble stearate is sodium stearate and/or potassium stearate;
the zinc-containing solid waste is steelmaking blast furnace ash;
the grain size of the zinc-containing solid waste is less than or equal to 0.1mm, and the content of CaO is 20 to 30 percent;
the aggregate is one or more of waste stone, tailings or coal gangue with the particle size of less than or equal to 5 mm.
2. The zinc-containing solid waste-based mining cementitious filler according to claim 1, characterized in that the water reducing agent comprises one or more of lignosulfonate, naphthalene sulfonate or sulfamate.
3. The preparation method of the zinc-containing solid waste-based mine cemented filling material according to any one of claims 1 to 2, characterized by comprising the following steps:
mixing the portland cement, the zinc-containing solid waste, the aggregate and the water reducing agent to obtain a mixture A; mixing soluble stearate with water to obtain a mixture B; and (3) mixing the mixture A and the mixture B, and uniformly stirring to prepare the mine cemented filling material based on the zinc-containing solid waste.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348714A (en) * | 2016-08-30 | 2017-01-25 | 北京玉锦资源与环境技术研究院（有限合伙） | Cementing filling material for co-processing zinc-containing dangerous waste of mine and preparation method of cementing filling material |
| CN106966678A (en) * | 2017-04-05 | 2017-07-21 | 北京科技大学 | It is a kind of to cooperate with cemented filling material of solidification arsenic and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348714A (en) * | 2016-08-30 | 2017-01-25 | 北京玉锦资源与环境技术研究院（有限合伙） | Cementing filling material for co-processing zinc-containing dangerous waste of mine and preparation method of cementing filling material |
| CN106966678A (en) * | 2017-04-05 | 2017-07-21 | 北京科技大学 | It is a kind of to cooperate with cemented filling material of solidification arsenic and preparation method thereof |
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