CN106747636B - Mineral inorganic superfine foaming filling material and preparation method and use method thereof - Google Patents
Mineral inorganic superfine foaming filling material and preparation method and use method thereof Download PDFInfo
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- CN106747636B CN106747636B CN201611138886.1A CN201611138886A CN106747636B CN 106747636 B CN106747636 B CN 106747636B CN 201611138886 A CN201611138886 A CN 201611138886A CN 106747636 B CN106747636 B CN 106747636B
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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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
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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
- C04B28/06—Aluminous 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
- 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
Abstract
The invention provides a mining inorganic superfine foaming filling material which is prepared from the following raw materials in parts by weight: 8-18 parts of sulphoaluminate cement, 25-40 parts of bentonite, 3-10 parts of perlite, 30-45 parts of fly ash, 3-8 parts of foaming agent and 0.3-1 part of water reducing agent. The inorganic superfine foaming filling material for the mine is used for reinforcing broken gangue and loose coal rock mass in a coal mine and filling a goaf, a caving area and a roadway side, and has the characteristics of long-distance pumping, quick condensation, difficult cracking and environmental protection. The invention also provides a preparation method and a use method of the mineral inorganic superfine foaming filling material.
Description
Technical Field
The invention belongs to the technical field of filling in the coal mining process, and particularly relates to a mining inorganic superfine foaming filling material, and a preparation method and a use method thereof.
Background
China is rich in coal resources, coal is a main energy source of China and occupies a leading position in an energy structure, and the healthy, stable and continuous development of the coal industry is a major problem related to national energy safety.
The polyurethane polymer filling material used in the underground coal mine at present has poor flame retardance and high reaction temperature, and can bring great potential safety hazard to the production of the coal mine. The cement-based inorganic filling material is generally prepared from cement, fly ash, coal gangue and the like, has poor conveying performance, slow solidification, low strength and slow growth, and is not beneficial to the requirement of coal mine production.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the mineral inorganic superfine foaming filling material, which adopts sulphoaluminate cement, bentonite and fly ash as main materials and is supplemented with a foaming agent and a water reducing agent, and the obtained inorganic superfine foaming filling material is used for filling coal mines, has the characteristics of high fluidity, quick solidification, micro-expansion, high strength, environmental protection and the like, can replace an organic polymer chemical filling material, and can also replace a cement-based inorganic filling material. The invention also provides a preparation method and a use method of the mineral inorganic superfine foaming filling material.
The technical scheme adopted by the invention is as follows:
the mining inorganic superfine foaming filling material is composed of the following raw materials in parts by weight: 8-18 parts of sulphoaluminate cement, 25-40 parts of bentonite, 3-10 parts of perlite, 30-45 parts of fly ash, 3-8 parts of foaming agent and 0.3-1 part of water reducing agent.
The mining inorganic superfine foaming filling material comprises the following raw materials in parts by weight: 12-15 parts of sulphoaluminate cement, 35-40 parts of bentonite, 5-7 parts of perlite, 36-40 parts of fly ash, 4-5 parts of foaming agent and 0.5-1 part of water reducing agent.
The mining inorganic superfine foaming filling material comprises the following raw materials in parts by weight: 15 parts of sulphoaluminate cement, 37 parts of bentonite, 7 parts of perlite, 36 parts of fly ash, 4.5 parts of foaming agent and 0.5 part of water reducing agent.
The mining inorganic superfine foaming filling material provided by the invention is prepared by screening sulphoaluminate cement with the granularity of 40 microns reaching 95%.
The inorganic superfine foaming filling material for the mine, disclosed by the invention, is characterized in that the foaming agent is an animal protein foaming agent or a plant protein foaming agent.
The inorganic superfine foaming filling material for the mine, disclosed by the invention, is characterized in that the water reducing agent is calcium lignosulphonate.
The invention also provides a preparation method of the mineral inorganic superfine foaming filling material, which comprises the following steps: respectively grinding the sulphoaluminate cement, the bentonite, the perlite, the fly ash, the foaming agent and the water reducing agent to obtain raw materials with the granularity range of 40 mu m reaching more than 95 percent, then uniformly mixing the raw materials to obtain a uniformly dispersed composite powdery product, and packaging.
The preparation method of the inorganic superfine foaming filling material for the mine is characterized in that the mixing is carried out in a mixer for 10-20 min.
The invention also provides a using method of the mining inorganic superfine foaming filling material, which comprises the following steps: mixing the mineral inorganic superfine foaming filling material with water to obtain uniform slurry, and conveying the slurry to a part needing to be reinforced or filled in a pipeline conveying mode for filling.
The invention relates to a using method of a mining inorganic superfine foaming filling material, wherein the water and the filling material are mixed according to the weight ratio of 1: mixing at a ratio of 0.4-1.5.
The sulphoaluminate cement of the invention acts as a cementitious material; the bentonite has better plasticity and stronger cohesiveness; the invention utilizes the lubricity, the bonding sealing property, the thickening property and the gelling property of the bentonite, and has the function of increasing and adjusting the toughness of the filling material. The bentonite is harmless to human body and has good environmental protection performance. The bentonite and the foaming agent are cooperatively foamed by utilizing the water absorption and expansion characteristics of the bentonite.
Perlite is a light and multifunctional novel material, and has the characteristics of light apparent density, low thermal conductivity coefficient, good chemical stability, wide use temperature range, small moisture absorption capacity, no toxicity, no smell, fire prevention, sound absorption and the like.
The fly ash in the invention plays a role of a reinforcing agent of the filling material. The activated flyash has very strong water absorption, and can be used as low-grade cement, so that the dosage of cement in the filling material is greatly reduced (only 8-18%), and the filling cost is greatly reduced, and the comprehensive properties of filling slurry, such as durability, can be improved.
The foaming agent has strong hydration property, surface property and the like. Foaming is carried out as a surfactant in the present invention. The foaming agent is used in the filling material, so that the slurry consumption in the same space filling process is reduced, the cost is saved, and the filling material has the functions of simple preparation, light weight, crack resistance, heat preservation and the like, has a wide field application prospect, and has good economic benefits.
The water reducing agent is brown yellow powder, has the solid content of more than 90 percent, the water reducing rate of 12-25 percent, is nontoxic, tasteless and incombustible, has no corrosion damage to reinforcing steel bars, has obvious water reducing and dispersing effects, and can improve the impermeability, frost resistance, corrosion resistance and durability of the filling material.
The inorganic superfine foaming filling material for the mine is used for reinforcing broken gangue and loose coal rock mass in a coal mine and filling a goaf, a caving area and a roadway side, has the characteristics of long-distance pumping, quick condensation, difficult cracking and environmental protection, and has the following advantages:
1. the product of the invention is compounded by pure inorganic materials, and essentially has non-combustible and antistatic properties. Compared with flame retardant and antistatic properties obtained by adding a flame retardant and an antistatic agent into a chemical grouting material, the flame retardant and antistatic grouting material has the characteristics of high safety and low cost, and has good transportability and injectability after being prepared into slurry.
2. The product of the invention is composed of nontoxic and harmless pure inorganic materials, and the composition of the material determines that the material has no pollution to the surrounding environment such as water, soil, air and the like, and belongs to green and environment-friendly materials.
3. The product of the invention has the advantages of high strength increasing speed, high resistance increasing, large flow state, self-compaction and the like, and the solidified body formed after filling has the characteristics of quick solidification, no shrinkage, high strength and the like.
The preparation method of the inorganic superfine foaming filling material for the mine is simple to operate and low in cost.
The method for using the inorganic superfine foaming filling material for the mine needs less equipment and is easy to operate by workers.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example l
The mining inorganic superfine foaming filling material is composed of the following raw materials in parts by weight: 15 parts of sulphoaluminate cement, 37 parts of bentonite, 7 parts of perlite, 36 parts of fly ash, 4.5 parts of foaming agent and 0.5 part of water reducing agent, wherein the foaming agent is a vegetable protein foaming agent, and the water reducing agent is calcium lignosulfonate.
The preparation method of the mining inorganic superfine foaming filling material comprises the following steps: preparing raw materials according to a ratio, respectively grinding sulphoaluminate cement, bentonite, perlite, fly ash, a foaming agent and a water reducing agent to be fine, wherein the granularity range of each raw material is 40 mu m and reaches more than 95 percent, then uniformly mixing the raw materials to obtain a uniformly dispersed composite powdery product, and packaging the product; in order to accelerate the mixing efficiency, the mixing was carried out in a blender for 10 min.
The application method of the mining inorganic superfine foaming filling material comprises the following steps: the mining inorganic superfine foaming filling material is mixed with water, the water and the filling material are mixed according to the mass ratio of 1:0.8 to obtain uniform slurry, the slurry is conveyed to a part needing to be reinforced or filled in a pipeline conveying mode for filling, and a mold can be arranged to control the filling range if necessary.
Example 2
The mining inorganic superfine foaming filling material is composed of the following raw materials in parts by weight: 12 parts of sulphoaluminate cement, 37 parts of bentonite, 5 parts of perlite, 40 parts of fly ash, 5 parts of foaming agent and 1 part of water reducing agent, wherein the foaming agent is a vegetable protein foaming agent, and the water reducing agent is calcium lignosulfonate.
The preparation method of the mining inorganic superfine foaming filling material comprises the following steps: preparing raw materials according to a ratio, respectively grinding sulphoaluminate cement, bentonite, perlite, fly ash, a foaming agent and a water reducing agent to be fine, wherein the granularity range of each raw material is 40 mu m and reaches more than 95 percent, then uniformly mixing the raw materials to obtain a uniformly dispersed composite powdery product, and packaging the product; in order to accelerate the mixing efficiency, the mixing was carried out in a blender for 20 min.
The method for using the mining inorganic ultrafine foaming filling material comprises the following steps: the mining inorganic superfine foaming filling material is mixed with water, the water and the filling material are mixed according to the mass ratio of 1:1.2 to obtain uniform slurry, the slurry is conveyed to a part needing to be reinforced or filled in a pipeline conveying mode for filling, and a mold can be arranged to control the filling range if necessary.
Example 3
The mining inorganic superfine foaming filling material is composed of the following raw materials in parts by weight: 18 parts of sulphoaluminate cement, 40 parts of bentonite, 5 parts of perlite, 30 parts of fly ash, 6.7 parts of foaming agent and 0.3 part of water reducing agent, wherein the foaming agent is animal protein foaming agent, and the water reducing agent is calcium lignosulfonate.
The preparation method of the inorganic ultrafine foam filling material for mine in this embodiment is the same as that in embodiment 1.
The method for using the mineral ultrafine inorganic foam filling material in the embodiment is the same as that in embodiment 1.
Example 4
The mining inorganic superfine foaming filling material is composed of the following raw materials in parts by weight: 9 parts of sulphoaluminate cement, 27 parts of bentonite, 10 parts of perlite, 45 parts of fly ash, 8 parts of foaming agent and 1 part of water reducing agent, wherein the foaming agent is a vegetable protein foaming agent, and the water reducing agent is calcium lignosulfonate.
The preparation method of the inorganic ultrafine foam filling material for mine in this embodiment is the same as that in embodiment 2.
The method for using the mineral inorganic ultrafine foam filling material in the embodiment is the same as the embodiment 2.
Example 5
The mining inorganic superfine foaming filling material is composed of the following raw materials in parts by weight: 8 parts of sulphoaluminate cement, 36 parts of bentonite, 10 parts of perlite, 40 parts of fly ash, 5 parts of foaming agent and 1 part of water reducing agent, wherein the foaming agent is a vegetable protein foaming agent, and the water reducing agent is calcium lignosulfonate.
The preparation method of the inorganic ultrafine foam filling material for mine in this embodiment is the same as that in embodiment 1.
The method for using the mineral ultrafine inorganic foam filling material in the embodiment is the same as that in embodiment 1.
The mining inorganic superfine foaming filling material prepared in the embodiment 1-5 is detected, the slump of filling slurry is 120-260 mm, the long-distance pumping can be realized, the longest horizontal pumping distance reaches 1200m, and the filling material is self-compacted after being pumped into a mold; demoulding after the filling is finished for 3-5 hours; the compression ratio is good at 5-10%, and the residual strength can reach 35-60% of the ultimate strength.
After the inorganic superfine foaming filling material for the mine, which is described in the embodiments 1-5, is adopted for pouring, the false setting phenomenon is generated after the slurry is stood for 5-10min, and the slurry is completely cured after more than 30 min. The reinforcing agent is used for reinforcing broken gangue and loose coal rock mass in a coal mine and filling a goaf, a caving area and a roadway side, and the main performance indexes of the reinforcing agent are shown in table 1.
TABLE 1 Main Performance indices of the mineral ultrafine inorganic foamed fillers described in examples 1 to 5
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (8)
1. An inorganic superfine foaming filling material for mining, which is characterized in that: the composition is characterized by comprising the following raw materials in parts by weight: 8-18 parts of sulphoaluminate cement, 25-40 parts of bentonite, 3-10 parts of perlite, 30-45 parts of fly ash, 3-8 parts of foaming agent and 0.3-1 part of water reducing agent; the foaming agent is an animal protein foaming agent or a plant protein foaming agent; the water reducing agent is calcium lignosulphonate.
2. The mining inorganic ultrafine foaming filling material according to claim 1, characterized in that: the composition is characterized by comprising the following raw materials in parts by weight: 12-15 parts of sulphoaluminate cement, 35-40 parts of bentonite, 5-7 parts of perlite, 36-40 parts of fly ash, 4-5 parts of foaming agent and 0.5-1 part of water reducing agent.
3. The mining inorganic ultrafine foaming filling material according to claim 1, characterized in that: the composition is characterized by comprising the following raw materials in parts by weight: 15 parts of sulphoaluminate cement, 37 parts of bentonite, 7 parts of perlite, 36 parts of fly ash, 4.5 parts of foaming agent and 0.5 part of water reducing agent.
4. The mining inorganic ultrafine foaming filling material according to claim 1, characterized in that: the granularity of the sulphoaluminate cement is screened, and 40 mu m of the sulphoaluminate cement reaches 95 percent.
5. The method for preparing the inorganic superfine foaming filling material for the mine according to any one of claims 1 to 4, which is characterized in that: the method comprises the following steps: preparing raw materials according to a ratio, respectively grinding sulphoaluminate cement, bentonite, perlite, fly ash, a foaming agent and a water reducing agent into fine powder, wherein the granularity range of each raw material is 40 mu m and reaches more than 95%, then uniformly mixing the raw materials to obtain a uniformly dispersed composite powdery product, and packaging.
6. The preparation method of the mining inorganic superfine foaming filling material according to claim 5, characterized in that: the mixing is carried out in a mixer for 10-20 min.
7. The use method of the mineral inorganic ultrafine foaming filling material of any one of claims 1 to 4, characterized in that: the method comprises the following steps: mixing the mineral inorganic superfine foaming filling material with water to obtain uniform slurry, and conveying the slurry to a part needing to be reinforced or filled in a pipeline conveying mode for filling.
8. The use method of the mining inorganic superfine foam filling material according to claim 7, characterized in that: the water and the filling material are mixed according to the ratio of 1: mixing at a ratio of 0.4-1.5.
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| CN107337412B (en) * | 2017-08-14 | 2019-11-22 | 山东安实绿色开采技术发展有限公司 | A kind of mining lightweight filler |
| CN110017167B (en) * | 2019-04-22 | 2022-08-19 | 安徽佳泰矿业科技有限公司 | Coal mine explosion-proof sealing wall and construction method thereof |
| CN111439976A (en) * | 2020-02-21 | 2020-07-24 | 阳泉煤业（集团）有限责任公司 | High-water filling material for gob-side entry retaining for mine and preparation method thereof |
| CN112456859B (en) * | 2020-12-18 | 2022-07-15 | 徐州中矿大贝克福尔科技股份有限公司 | Water reducing agent composition for coal mine paste filling and preparation method and application thereof |
| CN113683348A (en) * | 2021-07-29 | 2021-11-23 | 煤炭科学技术研究院有限公司 | Inorganic fire prevention and extinguishing filling material and preparation method thereof |
| CN114057455A (en) * | 2021-12-08 | 2022-02-18 | 北京窗口科技有限公司 | High-strength mineral-based inorganic injection filling material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4537633A (en) * | 1983-02-02 | 1985-08-27 | Suh Kyung Suk | Portland cement, process for preparing same, and compositions containing same |
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| CN102491690B (en) * | 2011-12-08 | 2013-04-17 | 河南理工大学 | Filling material for high caving area of coal roadway |
| CN103449837B (en) * | 2013-08-10 | 2015-05-27 | 安徽理工大学 | Mining foam paste filling material prepared by utilizing synergistic foaming method and preparation method thereof |
| CN105198329B (en) * | 2014-06-18 | 2017-09-22 | 阳泉市高星建材外加剂有限公司 | A kind of high water packing material and preparation method thereof and application method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4537633A (en) * | 1983-02-02 | 1985-08-27 | Suh Kyung Suk | Portland cement, process for preparing same, and compositions containing same |
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