CN114804714B - Expanding agent containing high-sulfur tailings and application method thereof - Google Patents
Expanding agent containing high-sulfur tailings and application method thereof Download PDFInfo
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- CN114804714B CN114804714B CN202210495344.9A CN202210495344A CN114804714B CN 114804714 B CN114804714 B CN 114804714B CN 202210495344 A CN202210495344 A CN 202210495344A CN 114804714 B CN114804714 B CN 114804714B
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- parts
- sulfur
- expanding agent
- tailings
- xanthan gum
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- 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
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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
Abstract
The invention relates to the field of building materials, in particular to an expanding agent containing high-sulfur tailings and an application method thereof, wherein the expanding agent containing the high-sulfur tailings comprises the following substances in parts by weight: 350-450 parts of fly ash, 100-200 parts of steel slag, 50-250 parts of high-sulfur tailing micro powder, 10-50 parts of nano silicon powder, 10-60 parts of lime, 1.5-2.0 parts of water reducing agent, 0.01-0.03 part of defoaming agent, 5-10 parts of exciting agent and 3-6 parts of stabilizing agent, wherein the exciting agent is a mixture of aluminum oxide, magnesium oxide and xanthan gum. The expanding agent has excellent expanding effect, can replace partial Portland cement in the process of preparing concrete, grouting material and filling material, improves the bleeding rate of the material and improves the later strength; the method also realizes effective recovery of the high-sulfur metal tailings, realizes secondary utilization of solid waste, avoids the problems of land resource occupation, environmental pollution, tailing dam collapse and the like caused by tailing accumulation, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to an expanding agent containing high-sulfur tailings, and a preparation method and application thereof.
Background
The tailings are solid mineral waste materials formed by naturally dehydrating tailing pulp discharged by a concentrating mill, and are also main components of solid industrial waste materials, and the tailings cannot be directly used for smelting due to low content of target components, but contain a large amount of mineral materials such as silicate, carbonate and the like, and can be used for preparing building materials such as concrete, grouting materials and the like after further treatment, so that the tailings are potential secondary resources.
The high-sulfur tailings are common tailings, but because the high-sulfur tailings contain a large amount of sulfur elements and have low reaction activity, building materials prepared from the high-sulfur tailings crack irregularly, the strength of the building materials is reduced, and the frost resistance, water permeability resistance and carbonization resistance of the building materials are also influenced to a certain extent.
Disclosure of Invention
The invention provides an expanding agent containing high-sulfur tailings and application thereof, aiming at the technical problems that the high-sulfur tailings in the prior art can not be effectively recycled and can not be effectively accumulated for a long time, so that environmental pollution and resource waste are caused.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
in one aspect, the embodiment of the invention provides a swelling agent containing high-sulfur tailings, which comprises the following substances in parts by mass: 350-450 parts of fly ash, 100-200 parts of steel slag, 50-250 parts of high-sulfur tailing micro powder, 10-50 parts of nano silicon powder, 10-60 parts of lime, 1.5-2.0 parts of water reducing agent, 0.01-0.03 part of defoaming agent, 5-10 parts of exciting agent and 3-6 parts of stabilizing agent, wherein the exciting agent is a mixture of aluminum oxide, magnesium oxide and xanthan gum.
Compared with the prior art, the expanding agent containing the high-sulfur tailings provided by the invention is used for preparing the ecological cementing material by using the steel slag, the nano silicon powder and the exciting agent with specific components: the steel slag has certain gelling activity and also contains a large amount of alkaline substances, the alkaline substances can generate synergistic action with calcium hydroxide generated by hydration of lime and magnesium hydroxide generated by hydration of a magnesium oxide component in an activator, the reaction activity of the high-sulfur tailing micro powder, the fly ash and the nano silicon powder is jointly excited, the dissolution of active silicon and active aluminum in the high-sulfur tailing, the fly ash and the nano silicon powder is promoted, the dissolved substances can generate a large amount of ettringite and gel minerals with expansion effects under the excitation action of sulfate radicals in the activator and the high-sulfur tailing, the shrinkage of grouting materials, concrete and filling materials is limited, the compactness of the materials is improved, the mechanical property of the materials is improved, xanthan gum in the activator can coat the materials such as the high-sulfur tailing and the nano silicon powder steel slag, the excessive expansion of the materials is limited while the hydration reaction is controlled, harmful ions can be adsorbed, and the durability of the materials is improved.
The concrete prepared by the expanding agent prepared from the raw materials in a concrete expanding agent experiment has an expansion rate of over 0.05% in water (7 days) and an expansion rate of over-0.01% in air (21 days), can reach the type II expanding agent standard specified in GB23439-2017 concrete expanding agent, can replace part of silicate cement in the process of preparing concrete, grouting materials and filling materials, reduces the using amount of cement in building materials, reduces the production cost, effectively recycles high-sulfur metal tailings, realizes secondary utilization of solid wastes, avoids the problems of land resource occupation, environmental pollution, tailing dam collapse and the like caused by tailing accumulation, and has a good application prospect.
Preferably, the mass ratio of the aluminum oxide to the magnesium oxide to the xanthan gum in the exciting agent is 2-5: 2 to 5:0.5 to 1.5.
The exciting agent consisting of the aluminum oxide, the magnesium oxide and the xanthan gum in a specific mass ratio is more matched with the composition of the expanding agent in the scheme, so that the exciting effect can be fully exerted in the expanding agent, and the negative influence of each component on the performance of the expanding agent is avoided: the alkaline substance magnesium hydroxide generated by hydration of magnesium oxide can further stimulate the reaction activity of the high-sulfur tailing micro powder, the fly ash and the nano silicon powder, and can also avoid volume expansion caused by magnesium hydroxide and expansion cracks; the xanthan gum can coat materials such as high-sulfur tailings, nano silicon powder steel slag and the like, can control hydration reaction, limit excessive expansion of the materials, adsorb harmful ions, improve the durability of the grouting material, and can reduce yield stress caused by the xanthan gum, and the reduction of the pumping performance of a system is brought by the increase of plastic viscosity.
Preferably, the xanthan gum is modified xanthan gum which contains methyl and unsaturated bonds and has a structure of D-mannose of a molecule grafted with vinyl pyrrolidone and hydroxyl grafted with cyanuric chloride.
Preferably, the preparation method of the modified xanthan gum specifically comprises the following steps:
s1: reacting xanthan gum with unsaturated organic acid under the catalysis of azobisisobutyronitrile at the temperature of 70-80 ℃ to prepare a xanthan gum derivative containing methyl and unsaturated bonds;
s2: and (2) mixing the xanthan gum derivative obtained in the step (S1) with vinyl pyrrolidone and cyanuric chloride, and grafting under the catalysis of formaldehyde and concentrated sulfuric acid to obtain the modified xanthan gum.
The modified xanthan gum containing methyl and unsaturated bonds and grafted with vinyl pyrrolidone in a D-mannose structure has more excellent performance, has outstanding adsorption capacity and more excellent coating performance on materials such as steel slag/high-sulfur metal tailing micro powder and the like, and can further improve the workability of a building material system.
Preferably, the stabilizer is a mixture of dibutyltin dilaurate, sodium tripolyphosphate and ammonium polyacrylate, and further preferably, the mass ratio of dibutyltin dilaurate, sodium tripolyphosphate and ammonium polyacrylate in the stabilizer is 1-1.5: 0.5 to 0.7:0.7 to 0.8.
Preferred stabilizer components are: dibutyltin dilaurate can play a catalytic role in the hydration reaction of the raw materials, and the activation energy required by the hydration reaction is reduced; the phosphate radical in the sodium tripolyphosphate can adjust the condensation time, the ammonium polyacrylate can be solidified with free water through hydrogen bonds, the workability of concrete is improved, the three can jointly guarantee the stability of an expanding agent system, and the application range of the expanding agent is expanded.
Preferably, SO in the high-sulfur tailing micro-powder 3 The content is 11-17%, and the specific surface area is 400-500m 2 /kg。
Preferred SO 3 The high-sulfur tailing micro powder with high content and specific surface area has a large amount of Si-O and Al-O broken bonds on the surface, the reaction activity is higher, the generation amount of ettringite can be increased, and the expansion rate of the expanding agent is further ensured.
Preferably, the specific surface area of the steel slag is 250-350 m 2 Kg, the specific surface area of the nano silicon powder is more than or equal to 1500m 2 /kg。
Preferably, the water reducing agent is a polycarboxylic acid water reducing agent, and the defoaming agent is an organic silicon defoaming agent.
The embodiment of the invention also provides the application of the expanding agent containing the high-sulfur tailings, and the expanding agent containing the high-sulfur tailings is used for replacing part of cement in concrete, grouting material and filling material; the optimal dosage of the concrete or the grouting material is 5 to 8 percent of the total amount of the cement; the dosage of the filling material is 6-10% of the total amount of the cement.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Examples 1 to 6
Examples 1 to 6 respectively provide an expanding agent containing high-sulfur tailings, and the raw materials of the expanding agent containing high-sulfur tailings in each example are shown in table 1:
TABLE 1
The preparation method of each swelling agent in examples 1 to 6 includes the steps of:
step 1: taking SO 3 Drying the high-sulfur tailings with the content of 11-17%, and ball-milling the dried high-sulfur tailings until the specific surface area is 400-500m 2 Per kg, storing the obtained high-sulfur tailing micro powder in a moisture-proof bag for later use; taking dibutyltin dilaurate, sodium tripolyphosphate and ammonium polyacrylate according to the formula amount, and uniformly mixing to obtain a stabilizer;
taking 10 parts of xanthan gum and 2.5 parts of methacrylic acid to react in a water bath kettle at 80 ℃ under the catalysis of 0.5 part of azobisisobutyronitrile to prepare a xanthan gum derivative containing methyl and unsaturated bonds; grafting 10 parts of xanthan gum derivatives, 2 parts of vinyl pyrrolidone and 1.5 parts of cyanuric chloride under the catalytic action of 0.5 part of formaldehyde and 0.2 part of concentrated sulfuric acid, further grafting the vinyl pyrrolidone in a D-mannose structure of the xanthan gum, introducing the cyanuric chloride on a hydroxyl group of a molecule, obtaining a modified xanthan gum which contains methyl and unsaturated bonds and is grafted with the vinyl pyrrolidone and the cyanuric chloride on the hydroxyl group in the D-mannose structure of the molecule, and uniformly mixing the obtained modified xanthan gum with aluminum oxide and magnesium oxide according to the formula amount to obtain an exciting agent;
and 2, step: weighing the fly ash and the specific surface area of 250-350 m according to the parts by weight 2 Per kg of steel slag, high-sulfur tailing micro powder and specific surface area more than or equal to 1500m 2 And mixing the nano silicon powder/kg and lime with a water reducing agent and a defoaming agent according to the formula ratio to obtain the expanding agent containing the high-sulfur tailings.
Comparative examples 1 to 7
Comparative examples 1 to 7 respectively provide the expanding agent containing the high-sulfur tailings, and the raw materials of the expanding agent containing the high-sulfur tailings in each comparative example are shown in table 2:
TABLE 2
Wherein: the expanding agent used in comparative example 3 is a conventional activator (a mixture of sodium hydroxide and sodium silicate in a mass ratio of 2; the stabilizer used in comparative example 6 was a common sulfonate-based stabilizer (sodium alkenyl sulfonate).
The preparation method of the expanding agent containing the high-sulfur tailings provided by each proportion keeps the same process as that in the embodiment 1 except that the types and the proportions of the raw materials are different from those in the embodiment 1.
Detection example:
the high-sulfur tailing-containing expanding agents prepared in examples 1 to 6 and comparative examples 1 to 7 are respectively used for preparing filling materials, grouting materials and concrete, wherein the compositions of the raw materials in the filling materials, the grouting materials and the concrete are shown in table 3:
table 3:
the expansion rate, the free bleeding rate and the compressive strength of filling materials, grouting materials and concrete prepared by using the expanding agent containing the high-sulfur tailings provided in examples 1 to 6 and comparative examples 1 to 7 as the expanding agent were tested, and the results are shown in tables 4 and 5:
TABLE 4
TABLE 5
The above description is intended to be illustrative of the present invention and should not be taken as limiting the invention, as the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. The expanding agent containing the high-sulfur tailings is characterized by comprising the following substances in parts by mass: 350-450 parts of fly ash, 100-200 parts of steel slag, 50-250 parts of high-sulfur tailing micro powder, 10-50 parts of nano silicon powder, 10-60 parts of lime, 1.5-2.0 parts of water reducing agent, 0.01-0.03 part of defoaming agent, 5-10 parts of exciting agent and 3-6 parts of stabilizing agent, wherein the exciting agent is a mixture of aluminum oxide, magnesium oxide and xanthan gum.
2. The expanding agent containing the high-sulfur tailings as claimed in claim 1, wherein the mass ratio of the alumina, the magnesium oxide and the xanthan gum in the exciting agent is 2-5: 2 to 5:0.5 to 1.5.
3. The swelling agent containing high-sulfur tailings as claimed in claim 1 or 2, wherein the xanthan gum is a modified xanthan gum which contains methyl and unsaturated bonds and has a structure of D-mannose of a molecule grafted with vinylpyrrolidone and hydroxyl group grafted with cyanuric chloride.
4. The swelling agent containing high-sulfur tailings of claim 3, wherein the preparation method of the modified xanthan gum comprises the following steps:
s1: reacting xanthan gum with unsaturated organic acid at a constant temperature of 70-80 ℃ under the catalysis of azobisisobutyronitrile to prepare a xanthan gum derivative containing methyl and unsaturated bonds;
s2: and mixing the xanthan gum derivative with vinyl pyrrolidone and cyanuric chloride, and grafting under the catalytic action of formaldehyde and concentrated sulfuric acid to obtain the modified xanthan gum.
5. The high sulfur tailings-containing expanding agent of claim 1, wherein the stabilizer is a mixture of dibutyltin dilaurate, sodium tripolyphosphate and ammonium polyacrylate.
6. The high-sulfur tailing-containing expanding agent according to claim 5, wherein the mass ratio of dibutyltin dilaurate, sodium tripolyphosphate and ammonium polyacrylate in the stabilizer is 1-1.5: 0.5 to 0.7:0.7 to 0.8.
7. The high-sulfur tailing-containing expanding agent according to claim 1, wherein SO in the micro powder of the high-sulfur tailings 3 The content is 11-17%, and the specific surface area is 400-500m 2 /kg。
8. The expanding agent containing high-sulfur tailings of claim 1, wherein the specific surface area of the steel slag is 250-350 m 2 Kg, the specific surface area of the nano silicon powder is more than or equal to 1500m 2 /kg。
9. The use of the expanding agent containing the high-sulfur tailings of any one of the claims 1 to 8, wherein the expanding agent containing the high-sulfur tailings is used for replacing cement in concrete, grouting materials and filling materials.
10. The application of the expanding agent containing the high-sulfur tailings as claimed in claim 9, wherein the amount of the expanding agent containing the high-sulfur tailings is 5% -8% of the total amount of the cement when the concrete and the grouting material are prepared; and/or
The amount of the expanding agent containing the high-sulfur tailings is 6-10% of the total amount of the cement when the filling material is prepared.
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| JP6812681B2 (en) * | 2016-07-04 | 2021-01-13 | 三菱瓦斯化学株式会社 | Leavening composition and leavening agent using it |
| CN109180060B (en) * | 2018-09-13 | 2021-06-08 | 江西鑫盛实业有限公司 | Enhanced concrete expanding agent and preparation method thereof |
| CN111018389A (en) * | 2019-12-09 | 2020-04-17 | 嘉华特种水泥股份有限公司 | Expanding agent clinker and production method thereof |
| CN112429986B (en) * | 2020-12-04 | 2022-03-01 | 武汉理工大学 | Full-solid-waste underground filling cementing material for high-sulfur tailings and preparation method thereof |
| CN113045226A (en) * | 2021-03-10 | 2021-06-29 | 中国新型建材设计研究院有限公司 | Low-cost solid waste base cementing material |
| CN114014578B (en) * | 2021-11-25 | 2023-02-03 | 中建商品混凝土江西有限公司 | Expanding agent based on industrial waste and preparation method thereof |
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Effective date of registration: 20230113 Address after: 244000 No.8, Aiguo Road, Tongguan District, Tongling City, Anhui Province Applicant after: Anhui Tongguan Industrial Technology Research Institute Co.,Ltd. Address before: 244000 Changjiang West Road, Anhui, Tongling Applicant before: TONGLING NONFERROUS METALS GROUP Co.,Ltd. Applicant before: University OF SCIENCE AND TECHNOLOGY BEIJING |
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Effective date of registration: 20230414 Address after: 244000 No.8, Aiguo Road, Tongguan District, Tongling City, Anhui Province Patentee after: Anhui Tongguan Industrial Technology Research Institute Co.,Ltd. Patentee after: University OF SCIENCE AND TECHNOLOGY BEIJING Address before: 244000 No.8, Aiguo Road, Tongguan District, Tongling City, Anhui Province Patentee before: Anhui Tongguan Industrial Technology Research Institute Co.,Ltd. |