CN116535181A - Cementing material composition and application thereof - Google Patents
Cementing material composition and application thereof Download PDFInfo
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- CN116535181A CN116535181A CN202310432721.9A CN202310432721A CN116535181A CN 116535181 A CN116535181 A CN 116535181A CN 202310432721 A CN202310432721 A CN 202310432721A CN 116535181 A CN116535181 A CN 116535181A
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000004568 cement Substances 0.000 claims abstract description 74
- 238000011049 filling Methods 0.000 claims abstract description 56
- 239000010881 fly ash Substances 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 30
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 30
- 239000004571 lime Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 30
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 26
- 239000011707 mineral Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 6
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 20
- 239000010440 gypsum Substances 0.000 abstract description 19
- 229910052602 gypsum Inorganic materials 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 9
- 239000011521 glass Substances 0.000 abstract description 9
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 abstract description 8
- 230000036571 hydration Effects 0.000 abstract description 7
- 238000006703 hydration reaction Methods 0.000 abstract description 7
- 229910001653 ettringite Inorganic materials 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 28
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 27
- 235000010755 mineral Nutrition 0.000 description 22
- 239000000292 calcium oxide Substances 0.000 description 15
- 235000012255 calcium oxide Nutrition 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011324 bead Substances 0.000 description 5
- 239000000378 calcium silicate Substances 0.000 description 5
- 229910052918 calcium silicate Inorganic materials 0.000 description 5
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000010436 fluorite Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000010754 BS 2869 Class F Substances 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
Classifications
-
- 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
- C04B28/14—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 calcium sulfate cements
- C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate 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
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a cementing material composition and application thereof, wherein the cementing material composition comprises the following raw materials in parts by mass: 30-40 parts of fly ash, 5-10 parts of fluorgypsum, 15-25 parts of cement, 30-40 parts of mineral powder and 2-7 parts of lime. The cementing material composition of the invention utilizes sulfuric acid and hydrofluoric acid in the fluorogypsum to activate fly ash, accelerates the surface rupture of glass bodies of the fly ash, promotes the active effect of the fly ash to be exerted as early as possible, and simultaneously, in the state that active substances in the fly ash react with cement and lime hydration products to generate calcium aluminate, gypsum reacts with the calcium aluminate for the second time to generate ettringite, thereby improving the compressive strength of the cementing body and greatly reducing the consumption of cement in mine filling.
Description
Technical Field
The invention relates to the technical field of cementing materials, in particular to a cementing material composition and application thereof.
Background
The fluorogypsum is a byproduct of preparing hydrofluoric acid by using fluorite and concentrated sulfuric acid, and 3.6 tons of anhydrous fluorogypsum are generated when 1 ton of hydrofluoric acid is produced. The specific production reaction equation is as follows:
H 2 SO 4 +CaF 2 →2HF↑+CaSO 4
when the fluorogypsum is discharged from the reaction furnace, the material temperature is 180-230 ℃, the gas temperature is 800-1000 ℃, and the discharged gypsum is anhydrous calcium sulfate, belonging to the type II CaSO 4 . The fluorine gypsum contains residual when the kiln is just taken outThe fluorite and sulfuric acid have higher contents of fluorine and sulfuric acid in the leaching solution, which exceed the limit value specified in hazardous waste identification standards, belong to harmful solid wastes with strong corrosiveness, and cannot be stacked.
For this, there are two general treatments in China: one is a lime neutralization method, namely, gypsum just discharged from a furnace is pulped by adding water, and the gypsum is put into lime for neutralization until the pH value is about 7 and discharged. The added lime neutralizes the sulfuric acid, further producing calcium sulfate. When lime is added, only a small amount of MgO is carried in, so by adopting the treatment method, the purity of the fluorine gypsum is high and can reach 80-90%, and the method is called lime-fluorine gypsum. The second is the bauxite neutralization process, i.e., the addition of bauxite to neutralize the remaining sulfuric acid can recover the useful product aluminum sulfate, making it slightly acidic, then adding lime to neutralize to ph=7, and then discharging for stacking. Bauxite contains about 40% of SiO 2 And other impurities, the grade of the finally discharged fluorine gypsum is reduced to 70-80%, and the gypsum is called bauxite-fluorine gypsum. At present, the annual output in China reaches more than 100 ten thousand tons. Most of the fluorine gypsum treatment is directly sent to a slag yard for piling, so that a large amount of land is required, the surrounding environment is maintained, and the fluorine gypsum treatment is a heavy burden of an enterprise. How to carry out comprehensive treatment and change waste into valuable becomes an important subject for enterprises.
In recent years, with the great increase of the national demands for nonferrous metals and the remarkable technical characteristics of the filling mining method, the specific gravity of the filling mining method is always in an increasing trend. In order to obtain good filling quality, many mines use portland cement as a filling cement. For a long time, a large number of underground goaf filling needs to consume tens of thousands of tons of cement materials, and according to statistics, 180-240 kg of cement is needed for each cubic meter of filling body, and the filling cost is 30-35 yuan for each 1t of ore to be extracted. Under the condition that nonferrous metals and gold prices slide down, the excessive filling cost not only causes great economic pressure on mines, but also influences the use and development of filling mining technology.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention aims to provide a cementing material composition which utilizes sulfuric acid and hydrofluoric acid in fluorogypsum to activate fly ash, accelerates the surface fracture of glass bodies of the fly ash, promotes the activity effect of the fly ash to be exerted as early as possible, and simultaneously, in the state that active substances in the fly ash react with cement and lime hydration products to generate calcium aluminate, gypsum reacts with the calcium aluminate for the second time to generate ettringite, thereby improving the compressive strength of the cementing body and greatly reducing the consumption of cement in mine filling.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a cementing material composition, which comprises the following raw materials in parts by mass: 30-40 parts of fly ash, 5-10 parts of fluorgypsum, 15-25 parts of cement, 30-40 parts of mineral powder and 2-7 parts of lime.
In some embodiments of the invention, the cement composition comprises the following raw materials in parts by mass: 35 parts of fly ash, 7 parts of fluorgypsum, 25 parts of cement, 30 parts of mineral powder and 3 parts of lime.
In some embodiments of the invention, the particle size of the fluorogypsum is 70-210 μm; the pH value of the fluorogypsum is 1.76-2.16.
In some embodiments of the invention, the pH of the fluorogypsum is 1.96.
In some embodiments of the present invention, the fluorogypsum comprises the following raw materials in percentage by mass: 4.82 to 7.26 percent of SiO 2 、1.71～2.54％Al 2 O 3 、25.43～39.53％CaO、2.31～3.52％MgO、39.43～61.31％SO 3 And the balance of ferric oxide.
In some embodiments of the present invention, the fluorogypsum comprises the following raw materials in percentage by mass: 6.03% SiO 2 、2.10％Al 2 O 3 、35.39％CaO、2.93％MgO、53.25％SO 3 0.3% ferric oxide.
In some embodiments of the invention, the fly ash is class ii class F fly ash.
In some embodiments of the invention, the cement is composed of the following raw materials in percentage by massThe method comprises the following steps: 54.62-70.64% CaO, 20.05-30.72% SiO 2 、8.34～12.36％Al 2 O 3 The D90 of the cement is 86-126 mu m.
In some embodiments of the invention, the cement is composed of the following raw materials in percentage by mass: 64.65% CaO, 25.03% SiO 2 、10.32％Al 2 O 3 The D90 of the cement is 106 μm.
In some embodiments of the invention, the mineral powder has a particle size distribution such that 9wt% of the particles have a particle size of less than 2.65 μm,35wt% of the particles have a particle size of less than 5.3 μm,53wt% of the particles have a particle size of less than 7.55 μm,65wt% of the particles have a particle size of less than 10.71 μm, and 90wt% of the particles have a particle size of less than 26.62 μm.
In some embodiments of the invention, the mineral powder is composed of the following raw materials in percentage by mass: 31.75 to 47.34 percent of SiO 2 、31.76～47.37％CaO、5.89～9.05％MgO、10.01～14.26％Al 2 O 3 1.03 to 1.64 percent of sulfur oxide and 0.34 to 0.50 percent of other oxides except sulfur oxide.
In some embodiments of the invention, the mineral powder is composed of the following raw materials in percentage by mass: 39.25% SiO 2 、39.36％CaO、7.43％MgO、12.22％Al 2 O 3 1.32% sulfur oxide, 0.42% oxides other than sulfur oxide.
In some embodiments of the invention, the lime is composed of the following raw materials in percentage by mass: 88.62-92.01% CaO, 4.52-6.93% MgO, 3.73-5.54% SiO 2 。
In some embodiments of the invention, the lime is composed of the following raw materials in percentage by mass: 89.6% CaO, 5.75% MGO, 4.65% SiO 2 。
The fly ash discharged from most of the power plants in China is low-calcium fly ash, the fly ash is not generally coagulated in a natural state, and under the condition of adding a proper amount of calcium oxide, thermodynamic analysis and practical application show that the fly ash can slowly react to generate calcium silicate gel and hydrated calcium aluminate for consolidation. However, the reaction is very slow, the reaction can be seen just after 28 days of hydration, and the advantages of the fly ash are only shown after 90 days of hydration. In practice, the hydration process of the fly ash is firstly the etching process of the calcium oxide on the surface of the glass body of the fly ash, and the etching process of the calcium oxide is relatively long because the structural body is relatively stable.
The mineral components in the fly ash mainly comprise quartz, mullite, mica, feldspar, hematite and the like, and the glass body in an amorphous phase is the main component of the fly ash. The glass body is in a bead shape, and comprises floating beads, hollow sinking beads, dense sinking beads, compound beads and the like; the glass body also contains loose and porous unburned carbon particles. The fly ash is a volcanic ash material with a certain activity, and from the chemical composition, the fly ash belongs to CaO-Al 2 O 3 ～SiO 2 The activity of the catalyst is mainly composed of SiO 2 And Al 2 O 3 Is determined by the content of (3).
The fluorgypsum is waste residue generated when fluorite powder and sulfuric acid are used for preparing hydrofluoric acid, and 3.5t of fluorgypsum is generated when 1t of hydrofluoric acid is produced. Under an optical microscope, the fluorogypsum is in a microcrystalline crystal shape, the microcrystals are tightly combined, the granularity is between 0.07 and 0.21mm, the longitudinal direction reaches 0.35mm, and other minerals are distributed in the fluorogypsum at intervals. When the fluorogypsum is discharged from the furnace, it is often 3% sulfuric acid and 1% hydrofluoric acid, so that the fluorogypsum has strong acidity ph=0.5 to 1.0. After the fly ash is mixed with the fluorogypsum, sulfuric acid and hydrofluoric acid firstly erode and dissolve the glass body, and especially the effect of the hydrofluoric acid on the glass body is particularly strong and the effect is most obvious. This promotes SiO in the fly ash 2 And Al 2 O 3 Is precipitated from hydrofluoric acid and SiO in fly ash 2 、Al 2 O 3 And alkali ions react:
SiO 2 +6HF→H 2 SiF 6 +2H 2 O
H 2 SiF 6 +2NaOH→Na 2 SiF 6 +2H 2 O
CaSiF 6 is faster than the general hydrated calcium silicate, and Na 2 SiF 6 The silicate hydration product is obviously promoted, and sulfuric acid reacts with active substances in the fly ash as follows:
SiO 2 +H + →H 2 SO 3
Al 2 O 3 +3H 2 SO 4 →Al 2 (SO 4 ) 3 +3H 2 O
the formation of silica gel and aluminum sulfate increases the chemical reaction capacity of the molecule. The reaction speed of silica gel and calcium hydroxide is far higher than that of SiO 2 The reaction speed between the calcium silicate hydrate and the calcium hydroxide is improved, and the generation of calcium silicate hydrate and the improvement of the strength of a hardening body are accelerated.
CaSO as the main component of fluorgypsum 4 With Al in fly ash 2 O 3 Reaction product 3CaO.Al with CaO 2 O 3 The ettringite is produced by the reaction.
3CaO·Al 2 O 3 +3(CaSO 4 ·2H 2 O)+25H 2 O→3CaO·Al 2 O 3 ·3CaSO 4 ·31H 2 O
Sometimes aluminum gel is generated, and under the condition of sufficient gypsum amount, ettringite is continuously generated by reaction, so that the reaction speed of ettringite is relatively high, the early strength of the fly ash cementing material is improved, and the filling is facilitated.
The fluorine gypsum has an activating effect on the fly ash, accelerates the surface fracture of the glass body of the fly ash, and promotes the activity effect of the fly ash to be exerted as early as possible; on the other hand, in the state that the active substances in the fly ash react with cement and lime hydration products to generate calcium aluminate, gypsum reacts with the calcium aluminate secondarily to generate ettringite, so that the early strength of the cementing body is improved.
Cement mainly plays a role in strengthening, and is a source of early strength of fly ash cementing materials.
Lime function: (1) hydrating to generate calcium hydroxide, making up the deficiency of calcium in the fly ash, and creating conditions for generating calcium silicate gel and calcium aluminate gel; (2) the pH in the solution was adjusted.
In a second aspect of the present invention, there is provided a method of preparing the cement composition, comprising the steps of:
s1, grinding and sieving the fluorogypsum to obtain fluorogypsum micro powder;
s2, mixing cement, mineral powder, fly ash, lime and the fluorine gypsum micropowder, and grinding to obtain the filling cementing material.
In some embodiments of the invention, in S1, the grinding speed is 300-500 r/min; the grinding time is 1-3 h.
In some embodiments of the invention, in S1, the grinding is at a speed of 400r/min; the milling time was 2h.
In some embodiments of the invention, in S1, the sieving is through a 100-300 mesh screen.
In some embodiments of the invention, in S1, the sieving is through a 200 mesh screen.
In some embodiments of the invention, in S2, the grinding speed is 80-120 r/min; the grinding time is 20-40 min.
In some embodiments of the invention, in S2, the grinding is at a speed of 100r/min; the grinding time is 30min.
In a third aspect of the invention, a filling cement is provided comprising fine tailings, water, and the cement composition.
In some embodiments of the invention, the mass ratio of the cement composition to the fine tailings is 1:10 to 15.
In some embodiments of the invention, the tailings consist of the following raw materials in mass percent: 33.215-43.215% SuO 2 、9.56～13.25％Al 2 O 3 、7.26～11.02％MgO、6.93～9.42％SO 3 、1.13～1.21％P 2 O 5 、6.04～8.63％Fe 2 O 3 、18.07～26.32％CaO、0.65～0.97％TiO 2 、0.24～0.32％BaO、1.42～2.19％PbO。
In some embodiments of the invention, the tailings consist of the following raw materials in mass percent: 38.215% SiO 2 、11.564％Al 2 O 3 、9.018％MgO、8.350％SO 3 、0.17％P 2 O 5 、7.308％Fe 2 O 3 、22.482％CaO、0.807％TiO 2 、0.283％BaO、1.803％PbO。
In some embodiments of the invention, the tailings have a particle size of 600 mesh or greater.
In some embodiments of the invention, the mass ratio of the pack cementation cement to fine tailings is 1:13.
In a fourth aspect of the present invention, a method for preparing a filling cement is provided, comprising the steps of:
and mixing the cementing material composition with fine tailings and water to obtain the filling cementing material.
In some embodiments of the invention, the solids content of the filled cement is 40 to 60%.
The beneficial effects of the invention are as follows:
the filling cementing material prepared by the invention can meet the filling requirement of mines, and has low material cost, and in addition, the compressive strength of the filling cementing material prepared by the invention can reach 2.33MPa, and exceeds the strength of the filling cementing material with the action of cement alone, so that the filling cementing material prepared by the invention can be used for low-concentration filling of mines.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were either commercially available from conventional sources or may be obtained by prior art methods unless specifically indicated. Unless otherwise indicated, assays or testing methods are routine in the art.
The raw materials used in examples and comparative examples include the following:
the cement is 425# ordinary Portland cement;
the mineral powder is blast furnace slag powder;
the fly ash is class II F fly ash;
the quicklime is high-calcium lime;
the tailings are fine tailings.
Example 1
The embodiment provides a filling cementing material, which comprises the following specific processes:
s1, adding 5 parts by mass of fluorogypsum into a small ball mill, putting a proper amount of standard small grinding balls, then starting the ball mill to ball mill for 2 hours at the speed of 400r/min (forward rotation for 1 hour and reverse rotation for 1 hour), and then sieving the ball-milled fluorogypsum powder with a 200-mesh sieve to obtain fluorogypsum micro powder;
s2, adding 20 parts by mass of cement, 30 parts by mass of mineral powder, 40 parts by mass of fly ash, 5 parts by mass of fluorine gypsum micropowder of S1 and lime into a planetary ball mill, ball milling at a speed of 100r/min for 30min (forward rotation for 15min and reverse rotation for 15 min), and crushing and uniformly mixing the powder to obtain a cementing material composition;
s3, adding the cementing material composition of S2 and fine tailings into a stirrer according to a mass ratio of ash to sand of 1:13, and stirring for 10min to uniformly mix the ash and the sand to obtain slurry; adding a proper amount of water to prepare slurry with the solid content of 50%, rapidly stirring for 10min, scraping the slurry around the pot wall into the pot, and stirring for 30s to obtain the filling cementing material.
Example 2
The present example provides a filling cement which differs from example 1 only in the mass fraction of the raw materials of the cement composition, and the specific process is:
the cementing material composition comprises the following raw materials in parts by weight: 20 parts by mass of cement, 35 parts by mass of mineral powder, 35 parts by mass of fly ash, 7 parts by mass of fluorgypsum and 3 parts by mass of lime.
Example 3
The present example provides a filling cement which differs from example 1 only in the mass fraction of the raw materials of the cement composition, and the specific process is:
the cementing material composition comprises the following raw materials in parts by weight: 25 parts by mass of cement, 30 parts by mass of mineral powder, 35 parts by mass of fly ash, 7 parts by mass of fluorgypsum and 3 parts by mass of lime.
Example 4
The present example provides a filling cement which differs from example 1 only in the mass fraction of the raw materials of the cement composition, and the specific process is:
the cementing material composition comprises the following raw materials in parts by weight: 23 parts by mass of cement, 31 parts by mass of mineral powder, 36 parts by mass of fly ash, 6 parts by mass of fluorgypsum and 4 parts by mass of lime.
Example 5
The present example provides a filling cement which differs from example 1 only in the mass fraction of the raw materials of the cement composition, and the specific process is:
the cementing material composition comprises the following raw materials in parts by weight: 15 parts by mass of cement, 40 parts by mass of mineral powder, 35 parts by mass of fly ash, 6 parts by mass of fluorgypsum and 4 parts by mass of lime.
Example 6
The present example provides a filling cement which differs from example 1 only in the mass fraction of the raw materials of the cement composition, and the specific process is:
the cementing material composition comprises the following raw materials in parts by weight: 22 parts by mass of cement, 34 parts by mass of mineral powder, 30 parts by mass of fly ash, 7 parts by mass of fluorgypsum and 7 parts by mass of lime.
Comparative example 1
The comparative example provides a filling cementing material which is different from the cementing material in example 1 only in the mass parts of the raw materials of the cementing material composition, and the concrete process comprises the following steps:
the cementing material composition comprises the following raw materials in parts by weight: 25 parts by mass of cement, 40 parts by mass of mineral powder, 30 parts by mass of fly ash, 2 parts by mass of fluorgypsum and 3 parts by mass of lime.
Comparative example 2
The comparative example provides a filling cementing material which is different from the cementing material in example 1 only in the mass parts of the raw materials of the cementing material composition, and the concrete process comprises the following steps:
the cementing material composition comprises the following raw materials in parts by weight: 20 parts by mass of cement, 40 parts by mass of mineral powder, 30 parts by mass of fly ash, 3 parts by mass of fluorgypsum and 7 parts by mass of lime.
Comparative example 3
The comparative example provides a filling cementing material which is different from the cementing material in example 1 only in the mass parts of the raw materials of the cementing material composition, and the concrete process comprises the following steps:
the cementing material composition comprises the following raw materials in parts by weight: 20 parts by mass of cement, 30 parts by mass of mineral powder, 30 parts by mass of fly ash, 15 parts by mass of fluorgypsum and 15 parts by mass of lime.
Comparative example 4
The comparative example provides a filling cementing material which is different from the cementing material in example 1 only in the mass parts of the raw materials of the cementing material composition, and the concrete process comprises the following steps:
the cementing material composition comprises the following raw materials in parts by weight: 15 parts by mass of cement, 30 parts by mass of mineral powder, 30 parts by mass of fly ash, 20 parts by mass of fluorine gypsum and 5 parts by mass of lime.
Comparative example 5
This comparative example provides a filling cement which is 425# portland cement.
Comparative example 6
This comparative example provides a filling cement which differs from example 1 only in the raw materials and parts by weight of the cement composition by the following specific procedures:
the cementing material composition comprises the following raw materials in parts by weight: 20 parts by mass of cement, 40 parts by mass of mineral powder, 33 parts by mass of fly ash and 7 parts by mass of lime.
Comparative example 7
This comparative example provides a filling cement which differs from example 1 only in the raw materials and parts by weight of the cement composition by the following specific procedures:
the cementing material composition comprises the following raw materials in parts by weight: 25 parts by mass of cement, 39 parts by mass of mineral powder, 33 parts by mass of fly ash and 3 parts by mass of lime.
Comparative example 8
This comparative example provides a filling cement which differs from example 1 only in the raw materials and parts by weight of the cement composition by the following specific procedures:
the cementing material composition comprises the following raw materials in parts by weight: 25 parts by mass of cement, 62 parts by mass of mineral powder, 10 parts by mass of fluorgypsum and 3 parts by mass of lime.
Performance test:
the cement compositions of examples 1 to 6 and comparative examples 1 to 8 were poured into a standard triple test mold of 70.7.70.7.70.7 mm, three groups of samples were poured into each group to obtain test pieces, the test pieces were placed into a standard curing box having a temperature of 20℃and a relative humidity of 90%, the test pieces were released after curing for 72 hours, the test pieces were again placed into the curing box to be cured to the corresponding age, the 28-day strength was measured at a speed of 10N/s by a full-automatic pressure tester, 3 test pieces were measured for each age, and the average value thereof was taken as the uniaxial compressive strength of the filler for the age, and the results are shown in Table 1.
Table 1. Compressive strength test results for the filled cements of examples 1-6 and comparative examples 1-8.
| Sample of | 28 day strength (MPa) |
| Example 1 | 1.79 |
| Example 2 | 2.04 |
| Example 3 | 2.33 |
| Example 4 | 1.85 |
| Example 5 | 1.68 |
| Example 6 | 1.79 |
| Comparative example 1 | 1.05 |
| Comparative example 2 | 1.21 |
| Comparative example 3 | 0.43 |
| Comparative example 4 | 0.35 |
| Comparative example 5 | 2.15 |
| Comparative example 6 | 0.33 |
| Comparative example 7 | 0.54 |
| Comparative example 8 | 0.67 |
As can be seen from table 1: the compressive strength of the filling cementing materials prepared in the embodiments 1 to 6 is greater than 1.5MPa, and for mine filling, the compressive strength of the filling cementing materials only needs to meet the requirement that the compressive strength is greater than 1.5MPa for 28 days, and collapse is not caused in the later stage of a mine, so that the filling cementing materials prepared in the invention can meet the mine filling requirement. In addition, the compressive strength of the filling cementing material prepared in the embodiment 3 of the invention is 2.33MPa, which exceeds the strength of the filling cementing material used for single cement action, so that the filling cementing material prepared in the invention can be used for low-concentration filling of mines.
The filling cementing material prepared by the invention meets the requirement of low-concentration filling for mines, and meanwhile, the cement consumption is 15-25% of that of single-purpose filling with cement, so that the filling cost is greatly saved, the used materials are solid waste materials, the purpose of green filling can be achieved, the mining cost is greatly saved for mine enterprises, and an effective consumption mode is found for the solid waste enterprises.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The cementing material composition is characterized by comprising the following raw materials in parts by mass: 30-40 parts of fly ash, 5-10 parts of fluorgypsum, 15-25 parts of cement, 30-40 parts of mineral powder and 2-7 parts of lime.
2. The cement composition according to claim 1, wherein the particle size of the fluorogypsum is 70 to 210 μm and the pH of the fluorogypsum is 1.76 to 2.16.
3. The cement composition according to claim 1, wherein the fluorogypsum comprises the following raw materials in mass percent: 4.82 to 7.26 percent of SiO 2 、1.71～2.54％Al 2 O 3 、25.43～39.53％CaO、2.31～3.52％MgO、39.43～61.31％SO 3 And the balance of ferric oxide.
4. The cement composition of claim 1, wherein the fly ash is class ii F fly ash.
5. The cement composition according to claim 1, wherein the mineral powder has a particle size distribution such that 9wt% of the particles have a particle size of less than 2.65 μm,35wt% of the particles have a particle size of less than 5.3 μm,53wt% of the particles have a particle size of less than 7.55 μm,65wt% of the particles have a particle size of less than 10.71 μm, and 90wt% of the particles have a particle size of less than 26.62 μm.
6. The cement composition according to claim 1, which isCharacterized in that the mineral powder consists of the following raw materials in percentage by mass: 31.75 to 47.34 percent of SiO 2 、31.76～47.37％CaO、5.89～9.05％MgO、10.01～14.26％Al 2 O 3 1.03 to 1.64 percent of sulfur oxide and 0.34 to 0.50 percent of other oxides except sulfur oxide.
7. A filling cement comprising fine tailings, water and a cement composition according to any of claims 1 to 6.
8. The filling cement according to claim 7, wherein the mass ratio of the cement composition according to any one of claims 1 to 6 to the fine tailings is 1:10 to 15.
9. The filling cement according to claim 7, wherein the fine tailings consist of the following raw materials in mass percent: 33.215-43.215% SiO 2 、9.56～13.25％Al 2 O 3 、7.26～11.02％MgO、6.93～9.42％SO 3 、1.13～1.21％P 2 O 5 、6.04～8.63％Fe 2 O 3 、18.07～26.32％CaO、0.65～0.97％TiO 2 0.24 to 0.32 percent of BaO and 1.42 to 2.19 percent of PbO; the grain size of the fine tailings is more than 600 meshes.
10. The method of preparing a filling cement according to any one of claims 7 to 9, comprising the steps of:
and mixing the cementing material composition with fine tailings and water to obtain the filling cementing material.
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