CN115849853A - Large-doped-amount fluorgypsum-based multielement solid waste filling cementing material and preparation method thereof - Google Patents
Large-doped-amount fluorgypsum-based multielement solid waste filling cementing material and preparation method thereof Download PDFInfo
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- 238000011049 filling Methods 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000002910 solid waste Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002893 slag Substances 0.000 claims abstract description 57
- 239000003607 modifier Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
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- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical compound [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229940037003 alum Drugs 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000010446 mirabilite Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 239000004568 cement Substances 0.000 abstract description 18
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
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- ZEMWIYASLJTEHQ-UHFFFAOYSA-J aluminum;sodium;disulfate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZEMWIYASLJTEHQ-UHFFFAOYSA-J 0.000 description 1
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Abstract
The invention discloses a large-doped fluorgypsum-based multielement solid waste filling cementing material and a preparation method thereof, wherein the cementing material is prepared by homogenizing and mixing 50-75 wt% of fluorgypsum, 4-10 wt% of carbide slag, 14-38 wt% of granulated blast furnace slag and 1-3 wt% of modifier, wherein the modifier is prepared by compounding sulfate, sodium methyl silicate and water glass. Compared with cement gelled materials, the gelled material of the invention has better filling performance, high early strength and low cost, does not attenuate later strength, and has better effect of resisting mine underground water corrosion.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a high-content fluorgypsum-based multielement solid waste filling cementing material and a preparation method thereof.
Background
The cemented filling mining method has the advantages of 'one waste treatment and two harm' and can improve the ore recovery rate and reduce the ore dilution rate,therefore, the method gradually becomes the preferred mining method for underground mining in China. Currently, the cementation used for underground filling of mines is mainly portland cement, especially p.o42.5 portland cement, but cement as a cementing material has two problems: firstly, the consolidation performance of materials with fine grain grade such as tailings, sandy soil and the like and high mud content is poor, the consumption of a filling body is large when the filling body reaches the design strength, the filling cost is high, and the proportion of cement cost in the filling cost is generally up to 60-80%; secondly, the cement filling slurry is easy to separate and bleed, and the cement loss is serious. In addition, cl which has a corrosive effect on the hydration products of the cementing materials in the filling bodies exists in the mine water in the goaf － 、SO 4 2－ 、Mg 2+ 、CO 3 2- Plasma, the filling body can be corroded by mine water after being filled into the goaf, the strength of the filling body is weakened, and further mining safety accidents are evolved, and such factors must be considered.
In the prior art, a patent with publication number CN 102633448A discloses a fluorgypsum-based cementing material for tailing filling and a preparation method thereof, wherein the cementing material is formed by mixing 97-99% of base material and 1-3% of sulfate excitant in percentage by mass, wherein the base material consists of 25-38% of modified fluorgypsum, 20-50% of slag, 0-25% of steel slag and 2-20% of cement clinker. The cementing material is used for tailing filling, the raw material source is wide, the process preparation is simple, the construction is convenient, the main material in the components is metallurgical solid waste residue with potential activity, but the consumption of the fluorgypsum in the cementing material is low, and the fluorgypsum needs to be ground until the specific surface area is 800m 2 More than kg, which has extremely high requirements on the performance of the grinding equipment and larger energy consumption, and is not beneficial to industrialized low-cost production.
In view of the above, it is necessary to design a large-doped fluorogypsum-based multi-element solid waste filling cementing material and a preparation method thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide a large-dosage fluorgypsum-based multielement solid waste filling cementing material which takes fluorgypsum as a main base material, combines carbide slag and granulated blast furnace slag and is supplemented with a small amount of modified material, overcomes the defect that the strength of a filling body formed by cementing tailing sand by using a novel cementing material which takes fluorgypsum as a main component (50 wt% -75 wt%) is weakened under mine water erosion in a goaf, and has high filling stability, good cementing effect, capability of resisting mine underground water corrosion and simple and easy processing technology, and a preparation method thereof.
In order to realize the purpose, the invention provides a large-doped fluorgypsum-based multielement solid waste filling cementing material, which comprises 50-75 wt% of fluorgypsum, 4-10 wt% of carbide slag, 14-38 wt% of granulated blast furnace slag and 1-3 wt% of modifier, wherein the modifier is prepared by compounding sulfate, sodium methyl silicate and water glass.
As a further improvement of the invention, the sulfate in the modifier is 15 to 40 weight percent, the sodium methyl silicate is 35 to 60 weight percent, and the water glass is 15 to 35 weight percent.
As a further improvement of the invention, the sulfate comprises any one or more of industrial mirabilite and alum.
The invention also provides a preparation method of the high-volume fluorgypsum-based multielement solid waste filling cementing material in any one of the technical schemes, which comprises the following steps: the composite material is prepared by homogenizing and mixing pretreated fluorgypsum 50-75 wt%, carbide slag 4-10 wt%, granulated blast furnace slag 14-38 wt% and modifier 1-3 wt%.
As a further improvement of the invention, the pretreatment operation of the fluorgypsum is as follows: grinding the fluorgypsum by a tube mill until the specific surface area is more than or equal to 300m 2 /kg。
As a further improvement of the invention, the pretreatment operation of the carbide slag comprises the following steps: grinding the carbide slag by a vertical mill until the specific surface area is more than or equal to 400m 2 /kg。
As a further improvement of the invention, the pretreatment operation of the granulated blast furnace slag is: grinding the granulated blast furnace slag through a vertical mill until the specific surface area is more than or equal to 400m 2 /kg。
As a further improvement of the invention, the carbide slag and the granulated blast furnace slag are measured in parts by weight, with their own water content being subtracted.
As a further improvement of the invention, the pretreatment operation of the modifier is as follows: grinding the modifier through a tube mill until the specific surface area is more than or equal to 300m 2 /kg。
As a further improvement of the invention, the homogenizing and mixing operation is mixing by a powder homogenizer.
The beneficial effects of the invention are:
1. according to the invention, the sulfate, the sodium methyl silicate and the water glass are compounded to prepare the modifier, the use ratio of the modifier, the sulfate is utilized to promote the nucleation and the growth rate of the dihydrate gypsum crystal and change the growth habit of the dihydrate gypsum crystal, so that the dihydrate gypsum crystal is converted from a plate shape to a needle column shape, the microscopic gap in the tailing filling body is reduced, the corrosion of underground water is primarily resisted, meanwhile, insoluble resin films generated by the reaction of the sodium methyl silicate and weak acid radical ions in underground mine water and calcium silicate gel generated by the reaction of the water glass and hydration products of the fluorgypsum are filled in the gap of the filling body, water molecules are further effectively prevented from entering the filling body, and the tailing filling body has good underground water corrosion resistance.
2. The method utilizes the strong basicity of the carbide slag to synthesize the acidity of the fluorgypsum and solidify soluble F, P impurities remained in the fluorgypsum, provides an alkaline environment required by depolymerization of a vitreous body structure in the slag, and enables the slag to release active silicon and aluminum components in the alkaline environment, wherein the active silicon forms hydrated calcium silicate under the action of calcium hydroxide, and the active aluminum, the alkaline component in the carbide slag and CaSO generated by hydration of the fluorgypsum 4 ·2H 2 The O reaction generates ettringite, thereby accelerating the hydration rate of the fluorgypsum, and simultaneously utilizing the modifier to convert the dihydrate gypsum crystal from a plate shape to a needle column shape, reducing the micro gap in the tailing filling body, and improving the hardened body phase composition and the micro gap structure, thereby leading the tailing filling body to have more compact micro structure and better cementing performance. In addition, compared with the cement for preparing the cementing material, the high-dosage fluorine of the inventionThe gypsum-based multi-element solid waste filling cementing material can consume more water in the hydration process to produce a large amount of needle-column-shaped dihydrate gypsum crystals to be filled in the gaps of the tailing filling body, so that the tailing filling body is more compact, and the hydrated calcium silicate (C-S-H) and ettringite generated by hydration of granulated blast furnace slag powder are matched, so that the tailing filling body has better cementation property, and the tailing filling body has higher early strength and continuously increased later strength.
3. The mine filling cementing material prepared by taking the industrial byproduct fluorgypsum as a main body has the advantages of good stability, easily obtained raw materials, high cementing strength and low manufacturing cost, is an ideal choice for mine filling materials in areas with the waste, is simple in preparation method, does not need calcination and other operations, does not need to add high-economic-cost alkaline components such as lime, cement clinker, caustic soda and the like, is suitable for large-scale commercial production, takes solid wastes in chemical and metallurgical industries as raw materials, realizes the recycling of solid wastes, and has wide application prospects in the field of waste recycling, mine filling and environmental protection.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme of the present invention are shown, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a large-doping-amount fluorgypsum-based multielement solid waste filling cementing material which comprises 50-75 wt% of fluorgypsum, 4-10 wt% of carbide slag, 14-38 wt% of granulated blast furnace slag and 1-3 wt% of modifier, wherein the modifier is prepared by compounding 15-40 wt% of sulfate, 35-60 wt% of sodium methyl silicate and 15-35 wt% of water glass.
Specifically, the sulfate comprises one or more of industrial mirabilite and alum.
The invention also provides a preparation method of the high-volume fluorine gypsum-based multielement solid waste filling cementing material, which is formed by homogenizing and mixing pretreated 50-75 wt% of fluorine gypsum, 4-10 wt% of carbide slag, 14-38 wt% of granulated blast furnace slag and 1-3 wt% of modifier through a powder homogenizer.
Specifically, the preprocessing operation is: grinding fluorgypsum and modifier through a tube mill until the specific surface area is more than or equal to 300m 2 Per kg; grinding the carbide slag by a vertical mill until the specific surface area is more than or equal to 400m 2 Per kg; grinding the granulated blast furnace slag by a vertical mill until the specific surface area is more than or equal to 400m 2 /kg。
Specifically, when the carbide slag and the granulated blast furnace slag are measured according to the parts by weight, the moisture content of the carbide slag and the granulated blast furnace slag needs to be deducted.
The preparation method of the present invention is described below with reference to specific examples.
Example 1
The embodiment provides a preparation method of a high-doped fluorgypsum-based multielement solid waste filling cementing material, which is formed by homogenizing and mixing 55wt% of fluorgypsum, 6wt% of carbide slag, 37.5wt% of granulated blast furnace slag and 1.5wt% of modifier by a powder homogenizer, wherein the modifier is formed by compounding 20wt% of alum, 60wt% of sodium methyl silicate and 20wt% of water glass; grinding the fluorgypsum and the modifier through a tube mill until the specific surface area is 300m 2 Per kg; grinding the carbide slag by a vertical mill until the specific surface area is 400m 2 Per kg; the granulated blast furnace slag is ground by a vertical mill until the specific surface area is 400m 2 /kg。
Examples 2 to 3
Examples 2 to 3 provide a method for preparing a large-doped fluorgypsum-based multi-component solid waste filling cementing material, and compared with example 1, the content of fluorgypsum, carbide slag, granulated blast furnace slag and modifier in examples 2 and 3 is 65wt%, 7.5wt%, 25.7wt%, 1.8wt%, 75wt%, 8.5wt%, 14.4wt% and 2.1wt%, respectively, and the rest steps are the same as example 1, and are not repeated herein.
Comparative examples 1 to 4
Comparative examples 1 to 4 respectively provide a method for preparing a multi-component solid waste filling cementing material with a large amount of fluorine gypsum, and compared with example 1, the contents of alum, sodium methyl silicate and water glass in the modifiers of comparative examples 1 and 2 are respectively adjusted to 40wt%, 30wt% and 15wt%, 70wt% and 15wt%. The modifier of comparative example 3 was 40wt% alum and 60wt% water glass. In comparative example 4, no modifier was added and granulated blast furnace slag was used for supplementation. The rest of the steps are the same as those in embodiment 1, and are not described herein again.
Comparative example 5
Comparative example 5 provides a preparation method of a large-doped fluorgypsum-based multi-component solid waste filling cementing material, compared with examples 1-3, the cementing material is prepared by homogenizing and mixing 80wt% of fluorgypsum, 9wt% of carbide slag, 8.5wt% of granulated blast furnace slag and 2.5wt% of modifier through a powder homogenizer, and the rest steps are the same as those in example 1 and are not repeated.
Comparative example 6
Comparative example 6 provides a cement binder having a specific surface area of 381m available from southern Cement Ltd 2 The/kg P.O42.5 portland cement is a cementing material for mine tailing cemented filling at present.
The cement materials prepared in examples 1 to 3 and comparative examples 1 to 6 were subjected to a full-tailing filling slurry strength ratio test. The total tailings used in the test are tungsten, molybdenum and fluorite multi-metal total tailings, d10=3.02um, d50=31.08um, d90=118.91um and-20 um tailings particles account for 38.32%, and the total tailings belong to medium-fine tailings. Adding the prepared cementing material into full tailings according to the ash-sand ratio of 1/5, pouring the mixture into a mortar mixer for uniform mixing, adding water according to the concentration of 72wt%, stirring for 3min, pouring the stirred slurry into a selected test mold (70.7 mm multiplied by 70.7 mm), scraping and numbering the surface of the test mold after initial setting of filler slurry, sealing the test mold with a preservative film, placing the test mold into a standard curing chamber for curing, demolding after final setting, dividing the demolded test blocks into two groups, placing the two groups into a standard curing chamber for curing, wherein the water used by the first group of curing chamber is laboratory deionized water, the water used by the second group of curing chamber is mine underground gushing water, and the pH value is 7.62. Unconfined compressive strength tests were conducted by the age of the test (3 d, 7d, 28 d), three replicates were tested per test piece and the results averaged. The groundwater corrosion resistance coefficient K of the pack was measured as follows:
K＝f/F
in the formula: f is unconfined compressive strength of the filling body under the mine water maintenance, and the unit is MPa; f is the unconfined compressive strength of the filler under the maintenance of deionized water, and the unit is MPa.
The ash-sand ratio = cement mass/full tailings mass, and the filling slurry mass concentration = (cement mass + full tailings mass)/(cement mass + full tailings mass + water).
The cementing strength and the corrosion resistance of the filling bodies prepared from the cementing materials prepared in examples 1 to 3 and comparative examples 1 to 6 and the tailings were measured, and the results are shown in table 1.
Table 1 results of testing the cementation strength and the corrosion resistance of the fillers prepared in examples 1 to 3 and comparative examples 1 to 6.
As can be seen from table 1, the cement materials prepared in examples 1 to 3 and the tailings were used to prepare fillers, which all had better uniaxial compressive strength than the fillers prepared from p.o42.5 cement and the tailings at different curing ages, than the fillers prepared from comparative example 6. However, when the content of the fluorgypsum in the cementing material is increased to 80% (comparative example 5), the performance of the filling body is greatly reduced, the bonding strength of 28d is only 0.93MPa, the corrosion resistance of 28d is reduced to 0.71, and the bonding strength and the corrosion resistance are lower than those of the filling body prepared by P.O42.5 cement and tailings. Therefore, the mixing amount of the filling cementing material prepared by using the fluorgypsum is not more than 75 percent.
As can be seen from the examples 1 and the comparative examples 4, the modifier provided by the invention can effectively improve the resistance of the filler prepared from the fluorgypsum cementing material and the tailings to the corrosion of mine water, and the corrosion resistance is improved by 15-17%; and the compressive strength of the novel cementing material can be improved by 5-8 percent.
Compared with the comparative example 3 and the comparative examples 1-2, the modifier provided by the invention can effectively improve the resistance of the filling body to mine water corrosion, the sodium methyl silicate in the modifier has the optimal mixing amount range, and when the content of the sodium methyl silicate exceeds 60% (compared with the comparative example 2), although the corrosion resistance of the filling body is improved by 8-10%, the compressive strength is reduced by 4-8%; when the sodium methyl silicate content is less than 35% (comparative example 1), although the corrosion resistance of the novel cementing material is improved by 2-5%, the strength is reduced by 2-8%.
In summary, the invention discloses a large-doped fluorgypsum-based multielement solid waste filling cementing material and a preparation method thereof, which synthesizes acidity of fluorgypsum by using alkalinity of carbide slag, solidifies soluble F, P impurities remained in the fluorgypsum, provides alkaline environment required by depolymerization of vitreous body structure in slag, and enables the slag to release active silicon and aluminum components in the alkaline environment, wherein the active silicon forms hydrated calcium silicate under the action of calcium hydroxide, and the active aluminum is hydrated with the alkaline components in the carbide slag and the fluorgypsum to generate CaSO 4 ·2H 2 The O reaction generates ettringite, thereby accelerating the hydration rate of the fluorgypsum, and simultaneously utilizing the modifier to convert the dihydrate gypsum crystal from a plate shape to a needle column shape, reducing the micro gap in the tailing filling body, and improving the hardened body phase composition and the micro gap structure, thereby leading the tailing filling body to have more compact micro structure and better cementing performance. In addition, compared with the cementing material prepared by using cement, the high-doped fluorgypsum-based multielement solid waste filling cementing material disclosed by the invention can consume more water in the hydration process to produce a large amount of needle-column dihydrate gypsum crystals to be filled in the pores of the tailing filling body, so that the tailing filling body is more compact, and the hydrated calcium silicate (C-S-H) and ettringite generated by hydration of granulated blast furnace slag powder are matched, so that the cementing property is better, and the tailing is enabled to be more compactThe filling body has higher early strength and continuously increased later strength. The sulfate is utilized to promote the nucleation and growth rate of the dihydrate gypsum crystal and change the growth habit of the dihydrate gypsum crystal, so that the dihydrate gypsum crystal is converted from a plate shape into a needle-column shape, microscopic pores in the tailing filling body are reduced, the corrosion of underground water is primarily resisted, meanwhile, insoluble resin films generated by the reaction of the sodium methylsilicate and weak acid radical ions in underground mine water and calcium silicate gel generated by the reaction of water glass and a hydrated product of fluorgypsum are filled among the pores of the filling body, water molecules are further effectively prevented from entering the filling body, and the tailing filling body has good underground water corrosion resistance. The invention takes the solid wastes in the chemical and metallurgical industries as raw materials, realizes the resource utilization of the solid wastes, and has wide application prospect in the field of waste resource utilization, mine filling and environmental protection.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. The large-dosage fluorogypsum-based multi-element solid waste filling cementing material is characterized in that: comprises 50 to 75 weight percent of fluorgypsum, 4 to 10 weight percent of carbide slag, 14 to 38 weight percent of granulated blast furnace slag and 1 to 3 weight percent of modifier, wherein the modifier is formed by compounding sulfate, sodium methyl silicate and water glass.
2. The high-doped fluorgypsum-based multi-component solid waste filling cementing material of claim 1, which is characterized in that: the modifier comprises 15-40 wt% of sulfate, 35-60 wt% of sodium methyl silicate and 15-35 wt% of water glass.
3. The high-doped fluorgypsum-based multi-component solid waste filling cementing material of claim 2, which is characterized in that: the sulfate comprises one or more of industrial mirabilite and alum.
4. A method for preparing the high-content fluorgypsum-based multielement solid waste filling cementing material as claimed in any one of claims 1 to 3, which is characterized in that: the composite material is prepared by homogenizing and mixing pretreated fluorgypsum 50-75 wt%, carbide slag 4-10 wt%, granulated blast furnace slag 14-38 wt% and modifier 1-3 wt%.
5. The preparation method of the high-dosage fluorogypsum-based multi-element solid waste filling cementing material according to claim 4, which is characterized in that: the pretreatment operation of the fluorgypsum is as follows: grinding the fluorgypsum by a tube mill until the specific surface area is more than or equal to 300m 2 /kg。
6. The preparation method of the high-dosage fluorogypsum-based multi-element solid waste filling cementing material according to claim 4, which is characterized in that: the pretreatment operation of the carbide slag comprises the following steps: grinding the carbide slag by a vertical mill until the specific surface area is more than or equal to 400m 2 /kg。
7. The preparation method of the high-volume fluorine gypsum based multielement solid waste filling cementing material as claimed in claim 6, characterized in that: the pretreatment operation of the granulated blast furnace slag comprises the following steps: grinding the granulated blast furnace slag through a vertical mill until the specific surface area is more than or equal to 400m 2 /kg。
8. The preparation method of the high-doped fluorgypsum-based multi-component solid waste filling cementing material according to claim 7, which is characterized in that: and when the carbide slag and the granulated blast furnace slag are measured according to the parts by weight, the moisture content of the carbide slag and the granulated blast furnace slag needs to be deducted.
9. The heavily doped fluorogypsum-based multi-element solid waste fill of claim 4The preparation method of the cementing material is characterized by comprising the following steps: the pretreatment operation of the modifier comprises the following steps: grinding the modifier through a tube mill until the specific surface area is more than or equal to 300m 2 /kg。
10. The preparation method of the high-dosage fluorogypsum-based multi-element solid waste filling cementing material according to claim 4, which is characterized in that: the homogenizing and mixing operation is mixing by a powder homogenizing machine.
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