CN111635203A - Cementing material and preparation method thereof, and sylvite tailing filling material and preparation method thereof - Google Patents
Cementing material and preparation method thereof, and sylvite tailing filling material and preparation method thereof Download PDFInfo
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- CN111635203A CN111635203A CN202010618317.7A CN202010618317A CN111635203A CN 111635203 A CN111635203 A CN 111635203A CN 202010618317 A CN202010618317 A CN 202010618317A CN 111635203 A CN111635203 A CN 111635203A
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- sylvite
- cementing material
- cementing
- filling material
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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
- C04B28/10—Lime cements or magnesium oxide cements
- C04B28/12—Hydraulic lime
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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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- 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
- C04B2111/00474—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
- 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
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
-
- 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
- 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 technical field of mine filling, and particularly discloses a cementing material and a preparation method thereof, and a sylvite tailing filling material and a preparation method thereof. The cementing agent comprises the following components in parts by weight: 3-5 parts of silicate cement clinker, 30-40 parts of quick lime, 60-70 parts of limestone, 5-10 parts of early strength agent and 2-4 parts of additive; the sylvite tailing filling material prepared by the cementing material comprises the following components in parts by weight: 8.5-9.5 parts of cementing material, 8-9 parts of sylvite mine tailings and 9-10 parts of sylvite brine mother liquor. The cementing material can directly replace a Portland cement binder used in the traditional metal mine backfill filling method, and the manufacturing cost of the filling material is obviously reduced. The cementing material is particularly suitable for backfilling a solid sylvite goaf, and after the cementing material is mixed with sylvite tailings and sylvite brine mother liquor, the compressive strength and the corrosion resistance of the filling material can be remarkably improved.
Description
Technical Field
The invention relates to the technical field of mine filling, in particular to a cementing material and a preparation method thereof, and a sylvite tailing filling material and a preparation method thereof.
Background
The solid sylvite ore at the present stage mainly comes from salt lake brine evaporation and underground mining. After mineral separation, a large amount of tailings (rich in sodium chloride) and brine mother liquor (rich in magnesium chloride) are obtained from soluble sylvite ores mined from the underground. The tailings have the characteristic of quick water solubility, and are easy to dissolve into ground water (rivers, lakes and reservoirs) after leaching or moisture absorption to further cause ecological environment disasters, and if the concentrated ground stacking is carried out, a large-area indoor tail salt shed needs to be built, and a large amount of land is occupied. Meanwhile, the brine mother liquor cannot be directly discharged due to the large amount of magnesium chloride. In addition, the mining engineering of the sylvite mine is dry mining, a goaf is inevitably formed, some ore layers are shallow from the ground, uncertain factors of rock salt stability change are more, normal mining of the underground sylvite mine is guaranteed through backfilling, the recovery rate of the sylvite mine is improved, and the safety production requirement of underground mining of the underground buried sylvite mine is met.
The traditional metal mine backfilling and filling method in China generally adopts silicate cement as a binder and returns to a goaf together with tailings, and because the underground buried sylvite ore in the inland area has great difference with the metal mine, the by-product tailings are soluble salts and generate a large amount of brine mother liquor, the tailings of the sylvite ore are backfilled to ensure the normal mining of the underground sylvite ore and improve the recovery rate of the sylvite ore, and certain strength is ensured, so that the difficulty is great. Therefore, the traditional silicate cement method for backfilling metal mines is not suitable for backfilling underground soluble potassium salt mines, and the silicate cement is too large in using amount and poor in economic benefit. At present, the large-scale backfilling of the soluble solid tailings at home and abroad does not have a mature technology.
Disclosure of Invention
The invention provides a cementing material and a preparation method thereof, a sylvite tailing filling material and a preparation method thereof, aiming at the problems that the existing mining goaf backfilling method by utilizing the tailings of sylvite ores is difficult, the strength cannot be guaranteed and the backfilling technology is immature.
In order to achieve the purpose, the invention adopts the following technical scheme:
the cementing material comprises the following components in parts by mass:
3-5 parts of silicate cement clinker, 30-40 parts of quick lime, 60-70 parts of limestone, 5-10 parts of early strength agent, 1-3 parts of accelerating agent and 2-4 parts of additive;
the early strength agent comprises triethanolamine, sodium sulfate and calcium chloride in a mass ratio of 2-3:1-2: 3-5;
the additive comprises sodium hydroxymethyl cellulose, sodium silicate and potassium aluminate in a mass ratio of 10:5-7: 9-11.
Compared with the prior art, the cementing material provided by the invention can directly replace a Portland cement binder used in the traditional metal mine backfill filling method, saves a large amount of Portland cement materials, can obviously reduce the manufacturing cost of the filling material for goaf backfill, and can reduce the manufacturing cost by more than 70%. The cementing material is particularly suitable for backfilling a solid sylvite goaf, and after the cementing material is mixed with sylvite tailings and sylvite brine mother liquor, the compressive strength and the erosion resistance of a filling material using the sylvite tailings as a raw material can be remarkably improved. The cementing material can be directly backfilled into a goaf of the sylvite ore with a filling material formed by mixing sylvite tailings and magnesium chloride-rich brine mother liquor.
The early strength agent in the cementing material comprises triethanolamine, sodium sulfate and calcium chloride in a specific proportion, wherein the addition of the triethanolamine can accelerate the coagulation strength of each component in the cementing material, but the addition of the triethanolamine in the cementing material can slow down the coagulation speed and the early strength of a filling material which takes the potassium salt mine tailings as raw materials; the invention can overcome the defect of adding triethanolamine by adding the sodium sulfate and the calcium chloride with a specific proportion into the cementing material, not only does not influence the coagulation speed of the cementing material, but also obviously improves the early strength of the cementing material. Addition of sodium sulfate makes tricalcium aluminate (C) in portland cement clinker3A) With SO4 2-And calcium hydroxide to form ettringite, consuming C3S hydration of released calcium hydroxide to C3Hydration of S is accelerated. Limestone is added though not participating in C3S hydration, but limestone and sodium sulfate can act synergistically to increase C significantly3Exothermic peak of S, accelerated C3The heat release rate of S. The addition of a specific amount of calcium chloride in the invention can excite the action effect of sodium sulfate and limestone, and greatly shorten C3Induction phase during hydration of SAnd the early strength of the cementing material is obviously improved. Therefore, the triethanolamine, the sodium sulfate and the calcium chloride are added according to a specific proportion, so that the coagulation strength and the early strength of the cementing material can be improved simultaneously, the addition of an accelerator is omitted, and the manufacturing cost of the cementing material is further reduced.
The admixture in the cementing agent of the present invention comprises sodium hydroxymethyl cellulose, sodium silicate and aluminic acid in a specific ratio. The combination of the potassium-hydroxymethyl-cellulose sodium, the sodium silicate and the potassium aluminate can obviously improve the dispersibility of silicate cement clinker, quicklime and limestone in the cementing material, avoid the aggregation or uneven distribution of the added filling aggregate and improve the strength uniformity of the filling material prepared by using the filling aggregate, and the combination of the potassium-hydroxymethyl-cellulose sodium, the sodium silicate and the potassium aluminate can obviously improve the inclusion of the soluble filling aggregate (sylvite mine tailings) and improve the erosion resistance, the impermeability, the crack resistance and the compressive strength of the filling material.
Preferably, the fineness of the portland cement clinker is 300-400 meshes.
Preferably, the fineness of the quicklime is 100-200 meshes.
Preferably, the fineness of the limestone is 200-300 meshes.
The invention also provides a preparation method of the cementing material. The preparation method at least comprises the following steps:
and respectively drying the portland cement clinker and the limestone, uniformly mixing the dried portland cement clinker and the limestone according to the mass ratio of each component of the cementing material, adding the quick lime, the early strength agent, the accelerating agent and the additive, and uniformly stirring to obtain the cementing material.
The invention also provides a sylvite tailing filling material which comprises the cementing material.
Preferably, the sylvite tailing filling material comprises the following components in parts by mass:
8.5-9.5 parts of cementing material, 8-9 parts of sylvite mine tailings and 9-10 parts of sylvite brine mother liquor.
Compared with the prior art, the sylvite tailing filling material provided by the invention is added with the cementing material with a specific content, so that the cementing material with a higher price can be replaced by the original cementing material, and the production cost is obviously reduced. The cementing material can form an air-hardening gel aggregate after being mixed with the sylvite brine mother liquor rich in magnesium chloride, can adapt to the alkaline environment of sylvite tailings, can stably exist for a long time, and meets the requirements of high strength and impermeability of goaf filling. The concretion formed by the filling material can also form high-strength adhesive concretion with the wall body of the sylvite goaf, so that the sylvite goaf can be effectively repaired, and the ground surface subsidence, water and soil resource loss and the like after the mine is mined are prevented. The filling material of the invention fully utilizes the toxic and harmful sylvite brine mother liquor and halogen salt tailings generated by exploiting sylvite ores, and the sylvite brine mother liquor and the halogen salt tailings can be directly used for underground filling after being mixed with the cementing material, thereby having higher popularization and application values.
The invention also provides a preparation method of the sylvite mine tailing filling material, which comprises the following steps: and crushing the potassium salt mine tailings, and then uniformly mixing the crushed potassium salt mine tailings with the cementing material and the potassium salt mine brine mother liquor to obtain the potassium salt mine brine.
The preparation method of the sylvite tailing filling material is simple, does not need special equipment requirements, and can be popularized and used.
Preferably, the granularity of the crushed potassium salt mine tailings is less than or equal to 5 mm.
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.
Example 1
The cementing material comprises the following components in parts by mass:
3 parts of silicate cement clinker, 30 parts of quick lime, 60 parts of limestone, 5 parts of early strength agent and 2 parts of additive;
wherein the early strength agent comprises triethanolamine, sodium sulfate and calcium chloride in a mass ratio of 2:1: 3; the additive comprises sodium hydroxymethyl cellulose, sodium silicate and potassium aluminate in a mass ratio of 10:5: 9; the fineness of the portland cement clinker is between 300-400 meshes; the fineness of the quicklime is between 100 and 200 meshes; the fineness of the limestone is between 200 and 300 meshes.
The preparation method of the cementing material comprises the following steps: respectively drying the portland cement clinker and the limestone, uniformly mixing the dried portland cement clinker and the limestone according to the mass ratio of each component of the cementing material, adding the quick lime, the early strength agent, the accelerating agent and the additive, and uniformly stirring to obtain the cementing material.
Example 2
The cementing material comprises the following components in parts by mass:
4 parts of silicate cement clinker, 35 parts of quicklime, 65 parts of limestone, 8 parts of early strength agent and 3 parts of additive;
wherein the early strength agent comprises triethanolamine, sodium sulfate and calcium chloride in a mass ratio of 5:3: 7; the additive comprises sodium hydroxymethyl cellulose, sodium silicate and potassium aluminate in a mass ratio of 5:3: 5; the fineness of the portland cement clinker is between 300-400 meshes; the fineness of the quicklime is between 100 and 200 meshes; the fineness of the limestone is between 200 and 300 meshes.
The preparation method of the cementing material comprises the following steps: respectively drying the portland cement clinker and the limestone, uniformly mixing the dried portland cement clinker and the limestone according to the mass ratio of each component of the cementing material, adding the quick lime, the early strength agent, the accelerating agent and the additive, and uniformly stirring to obtain the cementing material.
Example 3
The cementing material comprises the following components in parts by mass:
5 parts of silicate cement clinker, 40 parts of quick lime, 70 parts of limestone, 10 parts of early strength agent and 4 parts of additive;
wherein the early strength agent comprises triethanolamine, sodium sulfate and calcium chloride in a mass ratio of 3:2: 5; the additive comprises sodium hydroxymethyl cellulose, sodium silicate and potassium aluminate in a mass ratio of 10:7: 11; the fineness of the portland cement clinker is between 300-400 meshes; the fineness of the quicklime is between 100 and 200 meshes; the fineness of the limestone is between 200 and 300 meshes.
The preparation method of the cementing material comprises the following steps: respectively drying the portland cement clinker and the limestone, uniformly mixing the dried portland cement clinker and the limestone according to the mass ratio of each component of the cementing material, adding the quick lime, the early strength agent, the accelerating agent and the additive, and uniformly stirring to obtain the cementing material.
Example 4
The cementing material obtained in example 1 is used for preparing a sylvite tailing filling material, and the sylvite tailing filling material comprises the following components in parts by mass:
8.5 parts of cementing material, 8 parts of sylvite mine tailings and 9 parts of sylvite brine mother liquor.
The preparation method of the potash salt ore tailing filling material comprises the following steps: crushing the sylvite tailing until the granularity is less than or equal to 5mm, and then uniformly mixing the crushed sylvite tailing with cementing materials and sylvite brine mother liquor to obtain the sylvite brine.
Example 5
The cementing material obtained in example 2 is used for preparing a sylvite tailing filling material, and the sylvite tailing filling material comprises the following components in parts by weight:
9 parts of cementing material, 8.5 parts of sylvite tailing and 9.5 parts of sylvite brine mother liquor.
The preparation method of the potash salt ore tailing filling material comprises the following steps: crushing the sylvite tailing until the granularity is less than or equal to 5mm, and then uniformly mixing the crushed sylvite tailing with cementing materials and sylvite brine mother liquor to obtain the sylvite brine.
Example 6
The cementing material obtained in the embodiment 3 is used for preparing the sylvite tailing filling material, and the sylvite tailing filling material comprises the following components in parts by weight:
9.5 parts of cementing material, 9 parts of sylvite tailing and 10 parts of sylvite brine mother liquor.
The preparation method of the potash salt ore tailing filling material comprises the following steps: crushing the sylvite tailing until the granularity is less than or equal to 5mm, and then uniformly mixing the crushed sylvite tailing with cementing materials and sylvite brine mother liquor to obtain the sylvite brine.
Comparative example 1
The same amount of potassium chloride was used in place of calcium chloride in the early strength agent of example 1, and the other components and preparation method were the same as in example 1, to obtain a cement.
The potash salt tailing filling material was prepared using the above-mentioned cementing material, and the amount of the cementing material added and the method for preparing the potash salt tailing filling material were the same as in example 4.
Comparative example 2
The same amount of hydroxymethyl cellulose was used in place of the sodium hydroxymethyl cellulose in the admixture of example 1, and the other components and preparation method were the same as in example 1, to obtain a cement.
The potash salt tailing filling material was prepared using the above-mentioned cementing material, and the amount of the cementing material added and the method for preparing the potash salt tailing filling material were the same as in example 4.
The potassium salt ore tailing filling materials obtained in examples 4 to 6 and comparative examples 1 to 2 were tested for various properties, and the test results are shown in table 1:
TABLE 1 Properties of the Potassium salt mine tailings packing Material
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A cementing material is characterized in that: the paint comprises the following components in parts by mass:
3-5 parts of silicate cement clinker, 30-40 parts of quick lime, 60-70 parts of limestone, 5-10 parts of early strength agent and 2-4 parts of additive;
the early strength agent comprises triethanolamine, sodium sulfate and calcium chloride in a mass ratio of 2-3:1-2: 3-5;
the additive comprises sodium hydroxymethyl cellulose, sodium silicate and potassium aluminate in a mass ratio of 10:5-7: 9-11.
2. The cement of claim 1, wherein: the fineness of the portland cement clinker is 300-400 meshes.
3. The cement of claim 1, wherein: the fineness of the quicklime is 100-200 meshes.
4. The cement of claim 1, wherein: the fineness of the limestone is 200-300 meshes.
5. The method for preparing a binder according to any one of claims 1 to 4, wherein: and respectively drying the portland cement clinker and the limestone, uniformly mixing the dried portland cement clinker and the limestone according to the mass ratio of each component of the cementing material, adding the quick lime, the early strength agent, the accelerating agent and the additive, and uniformly stirring to obtain the cementing material.
6. The sylvite tailing filling material is characterized in that: comprising the binder of any one of claims 1-4.
7. The sylvite ore tailing filling material according to claim 6, wherein: the paint comprises the following components in parts by mass:
8.5-9.5 parts of cementing material, 8-9 parts of sylvite mine tailings and 9-10 parts of sylvite brine mother liquor.
8. The method for producing a sylvite ore tailing filling material according to claim 7, characterized in that: and crushing the potassium salt mine tailings, and then uniformly mixing the crushed potassium salt mine tailings with the cementing material and the potassium salt mine brine mother liquor to obtain the potassium salt mine brine.
9. The method for producing a sylvite ore tailing filling material according to claim 8, characterized in that: the granularity of the crushed potassium salt mine tailings is less than or equal to 5 mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010618317.7A CN111635203B (en) | 2020-07-01 | 2020-07-01 | Cementing material and preparation method thereof, and sylvite tailing filling material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010618317.7A CN111635203B (en) | 2020-07-01 | 2020-07-01 | Cementing material and preparation method thereof, and sylvite tailing filling material and preparation method thereof |
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| CN111635203A true CN111635203A (en) | 2020-09-08 |
| CN111635203B CN111635203B (en) | 2022-03-29 |
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Citations (5)
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|---|---|---|---|---|
| US20080066654A1 (en) * | 2006-09-14 | 2008-03-20 | Bj Services Company | Low density cements for use in cementing operations |
| CN104131836A (en) * | 2014-07-21 | 2014-11-05 | 云南省化工研究院 | Production method for underground potassic salt ore goaf backfilling |
| CN104193287A (en) * | 2014-09-09 | 2014-12-10 | 河北充填采矿技术有限公司 | High-strength quick-setting tailings cementing material and preparation method thereof |
| CN107365129A (en) * | 2017-09-01 | 2017-11-21 | 中农国际钾盐开发有限公司 | It is a kind of to utilize the method for being classified tail salt production sylvite ore cemented filling material |
| CN107619236A (en) * | 2017-09-30 | 2018-01-23 | 山东大学 | It is a kind of to be used for microfissure and the high-performance superfine cement based grouting material of powder fine sand soil grouting treatment and its application |
-
2020
- 2020-07-01 CN CN202010618317.7A patent/CN111635203B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080066654A1 (en) * | 2006-09-14 | 2008-03-20 | Bj Services Company | Low density cements for use in cementing operations |
| CN104131836A (en) * | 2014-07-21 | 2014-11-05 | 云南省化工研究院 | Production method for underground potassic salt ore goaf backfilling |
| CN104193287A (en) * | 2014-09-09 | 2014-12-10 | 河北充填采矿技术有限公司 | High-strength quick-setting tailings cementing material and preparation method thereof |
| CN107365129A (en) * | 2017-09-01 | 2017-11-21 | 中农国际钾盐开发有限公司 | It is a kind of to utilize the method for being classified tail salt production sylvite ore cemented filling material |
| CN107619236A (en) * | 2017-09-30 | 2018-01-23 | 山东大学 | It is a kind of to be used for microfissure and the high-performance superfine cement based grouting material of powder fine sand soil grouting treatment and its application |
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