CN113173746A - Geopolymer gel material based on copper tailings and preparation method thereof - Google Patents
Geopolymer gel material based on copper tailings and preparation method thereof Download PDFInfo
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- CN113173746A CN113173746A CN202110491239.3A CN202110491239A CN113173746A CN 113173746 A CN113173746 A CN 113173746A CN 202110491239 A CN202110491239 A CN 202110491239A CN 113173746 A CN113173746 A CN 113173746A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 78
- 239000010949 copper Substances 0.000 title claims abstract description 78
- 229920000876 geopolymer Polymers 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000003513 alkali Substances 0.000 claims abstract description 39
- 239000012190 activator Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000010881 fly ash Substances 0.000 claims abstract description 28
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011707 mineral Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 19
- 239000002002 slurry Substances 0.000 abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 8
- 239000011398 Portland cement Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 239000011083 cement mortar Substances 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011413 geopolymer cement Substances 0.000 description 2
- 229920003041 geopolymer cement Polymers 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010811 mineral waste Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 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
- C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
-
- 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
- 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)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a geopolymer gel material based on copper tailings and a preparation method thereof, wherein the adopted preparation method comprises the following steps: grinding and screening the sampled copper tailings, adding a modifier into the screened raw materials for modification, adding water glass into the composite powder, adding sodium hydroxide to change the modulus of the water glass, and uniformly stirring to obtain slurry; pouring the obtained slurry into a mold, performing vibration pressing molding, and curing for different curing times to obtain the geopolymer gel material. The invention is based on a geopolymer prepared by adding metakaolin and fly ash into copper tailings for modification and under the condition of an alkali activator; a large amount of copper tailings are treated, so that the environmental problems caused by the copper tailings and the fly ash are effectively solved; the efficiency of stabilizing the heavy metal solidification is high, and the time is short; the material has good mechanical properties; the compressive strength can reach 43.6Mpa under the condition of the optimal proportioning; is superior to the 42.5R grade of Portland cement in the general Portland cement (GB 175-2020).
Description
Technical Field
The invention belongs to the technical field of resource utilization of solid wastes, and particularly relates to a geopolymer gel material based on copper tailings and a preparation method thereof.
Background
Geopolymers are a new inorganic high polymeric gel material developed in recent years, first discovered and named by the french scientist Joseph Davidovits in the 20 th century; the development of geopolymers to present includes all three-dimensional network gel bodies which are prepared by polymerizing silicon-oxygen tetrahedron and aluminum-oxygen tetrahedron prepared by natural mineral or solid waste and have amorphous structures and quasi-static characteristics; the geopolymer is usually obtained by the strong alkali excitation of raw materials (such as fly ash, metakaolin, red mud, steel slag and the like) rich in silicon-aluminum components under certain conditions; such gel materials have excellent properties not possessed by cement: early strength, rapid hardening, good volume stability, chemical corrosion resistance, strong interface bonding capability, good impermeability, good high temperature resistance, good water and heat resistance, good durability and the like; countries such as the united states in the 80 th 20 th century have achieved stage results in the development field of such gel materials, and more than 30 countries and organizations have begun to establish research laboratories for such gel materials.
Copper tailings are solid waste materials left after copper ore is sorted into copper concentrate, native copper ore resources in China are relatively deficient, ore resources are low in grade (the copper grade is 1% -2%), concentrate is obtained through fine powder, flotation and other processes every year, a large amount of tailings are discharged, and accumulation damage of the tailings is mainly represented by air pollution caused by dust, heavy metal pollution of nearby farmlands caused by leachate, ecological damage of a large amount of accumulated farmlands and the like. Therefore, how to effectively solve the problem of copper tailings becomes an important subject in mining areas and in the front of the whole society.
At present, the utilization of copper tailings in China mainly comprises the following aspects: (1) re-selecting and recycling valuable components; according to related researches, only 25% of copper tailings in China have the value of recleaning and recycling, and a large amount of tailings still remain to be stockpiled after recleaning. (2) Concrete building materials such as baking-free bricks; because the content of heavy metal in the copper tailings is high, the copper tailings are made into baking-free brick building materials, wherein the heavy metal is not effectively solidified and stabilized, and the heavy metal can be leached into the environment to pollute the surrounding environment over time. (3) Preparing a high value-added product; the copper tailings can be used as a synthetic raw material of a silicon source material, such as production of white carbon black, quartz sand, a microcrystalline glass plate and the like, but the technical means for preparing the copper tailings into a high-added-value product is relatively complex, and the technical cost is relatively high.
The fly ash contains A certain amount of alkali and CaO, the activity of the two components can be effectively improved in A certain alkaline environment, the fly ash is easy to be excited by alkali liquor, the generation of N-A-S-H gel is facilitated, and simultaneously, hydration reaction can also occur to generate C-S-H gel (hydrated calcium silicate and hydrated aluminum silicate), so that the early strength of the product is improved. During the preparation of geopolymer cement, too high or too low of the Si/Al ratio provided by the raw material, i.e. high copper tailings or high metakaolin content, will reduce the degree of geopolymerization reaction and the strength of the resulting geopolymer cement. Meanwhile, the water glass component is too high, so that the amount of alkali brought in is increased, the condition that the generated N-A-S-H gel is corroded by too high alkalinity occurs, and the product strength is reduced.
The copper tailings are a composite material rich in mineral materials such as silicate, aluminate and the like and valuable elements, and are an important expression of a polymer gel material prepared by utilizing the copper tailings; has potential material preparation performance and economic value; the copper tailings are consolidated by steel slag, slag and fluorgypsum-based cementing materials such as Huangdaoquan, Houhao and the like of Wuhan university, and the strength of a tailing consolidation body 28d reaches 2.68 MPa. However, the related research reports on the preparation of the novel material, namely the geopolymer, by using the copper tailings are quite rare. The polymer prepared from the copper tailings can effectively solidify and stabilize the heavy metal content in the copper tailings, can realize better mechanical property, and has wide prospect when being used in various building industries.
Disclosure of Invention
In order to solve the problems, the invention provides a geopolymer gel material which is prepared by modifying copper tailings by adding metakaolin and fly ash and changing the modulus of water glass under the alkaline condition of NaOH under the alkaline excitation.
The geopolymer gel material is prepared from an alkali activator and composite minerals, wherein the composite minerals comprise 65-90% of copper tailings, 10-25% of metakaolin and 0-10% of fly ash.
Preferably, the alkali activator is prepared from deionized water, water glass and NaOH, wherein the modulus of the water glass is adjusted to be 0.8-1.6 by the NaOH.
Preferably, the alkali activator comprises, by mass, 20% -40% of deionized water, 0% -15% of NaOH and 25% -45% of water glass.
Preferably, the mass ratio of the alkali-activator to the composite mineral is 0.15-0.35.
Preferably, the copper tailings comprise the following components in percentage by weight: SiO22 30%～60%，Al2O3 8%～30%，CaO 10%～30%，MgO 0%～20% ，Fe2O3 0%～10%，K2O 0%～5%。
Preferably, the metakaolin contains SiO in percentage2 40%～60%，Al2O3 50%～80%，CaO 0%～5%，MgO 0%～5% ，Fe2O3 0%～3%，K2O 0%～3%。
Preferably, the percentage content of each component of the fly ash is SiO2 40%～60%，Al2O3 30%～60%，CaO 0%～10%，MgO 0%～5% ，Fe2O3 0%～3%，K2O 0%～3%。
A preparation method of a geopolymer gel material based on copper tailings comprises the following steps:
(1) uniformly mixing the dried, crushed and sieved raw materials according to a ratio to obtain a composite mineral;
(2) mixing Na2SiO3Mixing and stirring water and sodium hydroxide uniformly to prepare an alkali activator solution;
(3) adding an alkali activator solution into the composite mineral, mechanically stirring uniformly, filling into a mold, and pressing and molding at the pressure of 5-8 MPa;
(4) placing the sample and the mold in a curing box, curing for 30-36 h at 50-70 ℃, and then demolding;
(5) and (3) placing the demoulded sample into a constant-temperature constant-humidity curing box, and curing for 3d, 7d and 28d at the temperature of 30-50 ℃ and the humidity of 90-95%.
Preferably, the sieving is 200 mesh sieving.
Compared with the prior art, the invention has the beneficial effects that:
the geopolymer cementing material can be obtained by mixing the three raw materials and then adding alkali liquor, and performing stirring, pouring and curing processes, so that a large amount of copper tailings can be treated simultaneously, land resources occupied by solid waste stockpiling are reduced, and the environmental problem caused by the copper tailings and the fly ash is effectively solved; the copper tailings used in the invention contain high-content CaO, and the CaO can generate hydration reaction in the process of preparing the geopolymer, so that the mechanical property of the prepared geopolymer is greatly improved, and the geopolymer can partially replace an alkali activator, thereby reducing the dosage of the alkali activator and lowering the cost. More importantly, the heavy metal curing and stabilizing efficiency is high, and the time is short; has good mechanical properties, for example, the compressive strength can reach 43.6MPa under reasonable proportioning and proper curing conditions; the cement has a 42.5R grade superior to that of portland cement in general portland cement (GB 175-2020); provides a new idea for tailing solidification and mine filling, plays an important role in resource utilization of copper tailings, and shows a wide prospect in utilization of the construction industry.
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.
For the solution of the invention, the invention provides a preparation method of a geopolymer cementing material based on copper tailings, which comprises the following steps:
the method comprises the following steps: mixing and stirring copper tailings, metakaolin and fly ash to obtain a geopolymer raw material, wherein in the step, the content of each component S in the copper tailingsiO2 30%～60%，Al2O3 8%～30%，CaO 10%～30%，MgO 0%～20% ，Fe2O30%～10%，K20 to 5 percent of O. The metakaolin contains SiO in each component2 40%～60%，Al2O3 50%～80%，CaO 0%～5%，MgO 0%～5% ，Fe2O3 0%～3%，K20 to 3 percent of O. According to the preparation method of the geopolymer gel material based on the copper tailings, the alkali activator is prepared from deionized water, water glass and NaOH, wherein the modulus of the water glass is adjusted through the NaOH, so that the optimum excitation effect is achieved in the preparation of the geopolymer. According to the preparation method of the geopolymer gel material based on the copper tailings, the fly ash comprises SiO as each component in percentage2 40%～60%，Al2O3 30%～60%，CaO 0%～10%，MgO 0%～5% ，Fe2O3 0%～3%，K20 to 3 percent of O. According to the preparation method of the geopolymer gel material based on the copper tailings, the mass ratio of the alkali activator to the copper tailings, the metakaolin and the fly ash is 0.25-0.45, in the proportion range, the copper tailings, the metakaolin and the fly ash can enable raw materials to have proper Si/Al, so that the improvement of the geopolymerization reaction degree is facilitated, and the geopolymerization gel material with high strength is generated, wherein the copper tailings mainly provide Si components, and the metakaolin mainly provides Si and Al components.
Step 2: and adding an alkali activator into the composite powder raw material body, and uniformly stirring to obtain the neat paste. In the step, the alkali activator is prepared from deionized water, sodium hydroxide and water glass; the alkali activator comprises the following components in percentage by mass: 20-40% of deionized water, 0-15% of sodium hydroxide and 25-45% of water glass, preferably 36% of deionized water, 5% of sodium hydroxide and 35% of water glass; the mass ratio of the alkali activator to the composite powder raw material is 0.25-0.45. After being excited in a strong alkaline solution, the silicon-aluminum raw material generates a geological polymerization reaction to generate a novel amorphous cementing material with a three-dimensional network structure.
And step 3: and pouring the clean slurry into a mold, and performing vibration molding and room-temperature curing to obtain the geopolymer cementing material. In the step, the vibration molding is to vibrate the clean paddles in the mold for 4-6 min by using a cement mortar jolt ramming table; and the room-temperature curing is to seal the clean paddle and the mold after vibration molding, place the sample and the mold in a curing box, cure for 30-36 hours at 50-70 ℃, then demould, and then place the sample in a constant-temperature constant-humidity curing box, and cure for 3d, 7d and 28d at 30-50 ℃ and 90-95% humidity.
For the solution of the present invention, a geopolymer gelled material based on copper tailings is provided, and the geopolymer gelled material based on copper tailings is prepared by the method for preparing the geopolymer gelled material based on copper tailings in the foregoing solution.
The metakaolin and the fly ash can provide an Al source and adjust SiO2/Al2O3The ratio of (a) to (b), improving the strength of the product. Compounding sodium hydroxide and water glass into alkali liquor, wherein the alkali liquor can destroy Si-O bond and Al-O bond structures in raw materials to generate free silicon-oxygen tetrahedron and aluminum-oxygen tetrahedron monomers, and the monomer tetrahedron structures are migrated under the flowing of the solution to generate condensation polymerization reaction to generate N-A-S-H gel; the copper tailings and the fly ash contain high CaO content, and meanwhile, the volcanic ash reaction can occur to generate C-S-H gel, so that the obtained product has high compressive strength, A good excitation effect can be obtained within the proportion range, the cost is low, the poor excitation effect caused by too low alkalinity is avoided, the generated N-A-S-H gel is few, the generated N-A-S-H gel is corroded by too high alkalinity, and the cost is increased.
Example 1
Example 1 provides a preparation method of a geopolymer cementing material based on copper tailings, wherein the content of each component of the copper tailings in the example is SiO236.85 percent and Al2O3 8.27%，CaO 27.63%，MgO 3.65% ，Fe2O3 5.54%，K2O2.65%, the content of each component in metakaolin is SiO254.56%, Al2O3 43.67%，CaO 0.08%，MgO 0.40% ，Fe2O3 0.07%，K20.50 percent of O, 51.27 percent of fly ash and Al2O3 16.50%，CaO 2.80%，MgO 1.20% ，Fe2O3 7.10%，K21.30% of O, an alkali activator with a water glass modulus of 0.8 prepared by NaOH, and a ratio of the added alkali activator to the composite powder of 0.3, wherein the preparation method of the geopolymer comprises the following steps:
(1) and mixing 90 parts of copper tailings, 10 parts of metakaolin and 0 part of fly ash to obtain the geopolymer raw material composite powder.
(2) And adding 30 parts of alkali activator into the composite powder, adding 20 parts of deionized water, and stirring for 3min to obtain the pure slurry.
(3) Pouring the clean slurry into a 25 multiplied by 25mm mould, vibrating for 4min under a cement mortar vibrating table, placing the sample and the mould into a curing box for curing at 50 ℃ for 30h, then demoulding, and placing the demoulded sample into a constant-temperature constant-humidity curing box for curing at 30 ℃ and 90% humidity for 3d, 7d and 28d to obtain the geopolymer gelled material.
The geopolymer cementing material obtained by the method has the 3d compressive strength value of 6.7MPa, the 7d compressive strength value of 7.5MPa and the 28d compressive strength value of 11.9 MPa.
Example 2
Example 2 provides a preparation method of a geopolymer cementing material based on copper tailings, wherein the content of each component of the copper tailings in the example is SiO247.46 percent and Al2O3 8.54%，CaO 18.24%，MgO 2.35% ，Fe2O3 3.54%，K2O2.36 percent, wherein the contents of all components in metakaolin are the same as those in the example 1, the contents of all components in fly ash are the same as those in the example 1, an alkali activator with the water glass modulus of 1.0 is prepared by NaOH, the ratio of the added alkali activator to the composite powder is 0.3, and the preparation method of the geopolymer comprises the following steps:
(1) and mixing 85 parts of copper tailings, 10 parts of metakaolin and 5 parts of fly ash to obtain the geopolymer raw material composite powder.
(2) And adding 30 parts of alkali activator into the composite powder, adding 20 parts of deionized water, and stirring for 3min to obtain the pure slurry.
(3) Pouring the clean slurry into a 25 multiplied by 25mm mould, vibrating for 4min under a cement mortar vibrating table, placing the sample and the mould into a curing box, curing for 30h at 55 ℃, then demoulding, and placing the demoulded sample into a constant-temperature constant-humidity curing box, and curing for 3d, 7d and 28d at 35 ℃ and 90% humidity to obtain the geopolymer gelled material.
The geopolymer cementing material obtained by the method has the 3d compressive strength value of 8.9MPa, the 7d compressive strength value of 11.5MPa and the 28d compressive strength value of 13.7 MPa.
Example 3
Example 3 provides a preparation method of a geopolymer cementing material based on copper tailings, wherein the content of each component of the copper tailings in the example is SiO255.69%, and Al2O3 10.54%，CaO 9.53%，MgO 3.26% ，Fe2O3 2.37%，K2O2.38 percent, the contents of all components in metakaolin are the same as those in the example 1, the contents of all components in fly ash are the same as those in the example 1, an alkali activator with the water glass modulus of 1.2 is prepared by NaOH, the ratio of the added alkali activator to the composite powder is 0.3, and the preparation method of the geopolymer comprises the following steps:
(1) 80 parts of copper tailings, 15 parts of metakaolin and 5 parts of fly ash are mixed to obtain the geopolymer raw material composite powder.
(2) And adding 30 parts of alkali activator into the composite powder, adding 20 parts of deionized water, and stirring for 3min to obtain the pure slurry.
(3) Pouring the clean slurry into a 25 multiplied by 25mm mould, vibrating for 4min under a cement mortar vibrating table, placing the sample and the mould into a curing box, curing for 30h at 60 ℃, then demoulding, and placing the demoulded sample into a constant-temperature constant-humidity curing box, and curing for 3d, 7d and 28d at 40 ℃ and 90% humidity to obtain the geopolymer gelled material.
The geopolymer cementing material obtained by the method has the 3d compressive strength value of 11.6MPa, the 7d compressive strength value of 17.7MPa and the 28d compressive strength value of 19.5 MPa.
Example 4
Embodiment 4 provides a method for preparing a geopolymer cementing material based on copper tailings, in this example, the content of each component in the copper tailings is the same as that in example 3, the content of each component in metakaolin is the same as that in example 1, the content of each component in fly ash is the same as that in example 1, an alkali-activating agent with a water glass modulus of 1.4 is prepared by NaOH, the ratio of the added alkali-activating agent to the composite powder is 0.35, and the method for preparing the geopolymer comprises the following steps:
(1) 70 parts of copper tailings, 20 parts of metakaolin and 10 parts of fly ash are mixed to obtain the geopolymer raw material composite powder.
(2) And adding 35 parts of alkali activator into the composite powder, adding 20 parts of deionized water, and stirring for 3min to obtain the pure slurry.
(3) Pouring the clean slurry into a 25 multiplied by 25mm mould, vibrating for 4min under a cement mortar vibrating table, placing the sample and the mould into a curing box, curing for 35h at 65 ℃, then demoulding, and placing the demoulded sample into a constant-temperature constant-humidity curing box, and curing for 3d, 7d and 28d at 45 ℃ and 90% humidity to obtain the geopolymer gelled material.
The geopolymer cementing material obtained by the method has the 3d compressive strength value of 21.6MPa, the 7d compressive strength value of 26.8MPa and the 28d compressive strength value of 30.4 MPa.
Example 5
Embodiment 5 provides a method for preparing a geopolymer cementing material based on copper tailings, in this example, the content of each component in the copper tailings is the same as that in example 3, the content of each component in metakaolin is the same as that in example 1, the content of each component in fly ash is the same as that in example 1, an alkali-activating agent with a water glass modulus of 1.6 is prepared by NaOH, the ratio of the added alkali-activating agent to the composite powder is 0.35, and the method for preparing the geopolymer comprises the following steps:
(1) and mixing 65 parts of copper tailings, 25 parts of metakaolin and 10 parts of fly ash to obtain the geopolymer raw material composite powder.
(2) And adding 35 parts of alkali activator into the composite powder, adding 20 parts of deionized water, and stirring for 3min to obtain the pure slurry.
(3) Pouring the clean slurry into a 25 multiplied by 25mm mould, vibrating for 4min under a cement mortar vibrating table, placing the sample and the mould into a curing box, curing for 36h at 70 ℃, then demoulding, and placing the demoulded sample into a constant-temperature constant-humidity curing box, and curing for 3d, 7d and 28d at 50 ℃ and 90% humidity to obtain the geopolymer gelled material.
The geopolymer cementing material obtained by the method has the 3d compressive strength value of 34.7MPa, the 7d compressive strength value of 38.6MPa and the 28d compressive strength value of 43.6 MPa.
Compared with the prior art, the invention has the beneficial effects that:
the geopolymer cementing material can be obtained by mixing the three raw materials and then adding alkali liquor, and performing stirring, pouring and curing processes, so that a large amount of copper tailings can be treated simultaneously, land resources occupied by solid waste stockpiling are reduced, and the environmental problem caused by the copper tailings and the fly ash is effectively solved; the copper tailings used in the invention contain high-content CaO, and the CaO can generate hydration reaction in the process of preparing the geopolymer, so that the mechanical property of the prepared geopolymer is greatly improved, and the geopolymer can partially replace an alkali activator, thereby reducing the dosage of the alkali activator and lowering the cost. More importantly, the heavy metal curing and stabilizing efficiency is high, and the time is short; has good mechanical properties, for example, the compressive strength can reach 43.6MPa under reasonable proportioning and proper curing conditions; the cement has a 42.5R grade superior to that of portland cement in general portland cement (GB 175-2020); provides a new idea for tailing solidification and mine filling, plays an important role in resource utilization of copper tailings, and shows a wide prospect in utilization of the construction industry.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. The geopolymer gel material based on the copper tailings is characterized in that the gel material is prepared from an alkali activator and composite minerals, wherein the composite minerals comprise 65-90% of the copper tailings, 10-25% of metakaolin and 0-10% of fly ash.
2. The copper tailing based geopolymer gel material of claim 1, characterized in that the alkali-activator is formulated from deionized water, water glass, NaOH, wherein the water glass modulus is adjusted by NaOH to be in the range of 0.8-1.6.
3. The geopolymer gel material based on copper tailings as claimed in claim 1, wherein the alkali activator comprises 20-40% of deionized water, 0-15% of NaOH and 25-45% of water glass in percentage by mass.
4. The geopolymer gel material based on copper tailings as claimed in claim 1, wherein the mass ratio of the alkali-activating agent to the composite mineral is 0.15-0.35.
5. The geopolymer gel material based on copper tailings as claimed in claim 1, wherein the percentage content of each component in the copper tailings is as follows: SiO22 30%～60%，Al2O3 8%～30%，CaO 10%～30%，MgO 0%～20% ，Fe2O30%～10%，K2O 0%～5%。
6. The geopolymer gel material based on copper tailings of claim 1, wherein the metakaolin comprises SiO in percentage of each component2 40%～60%，Al2O3 50%～80%，CaO 0%～5%，MgO 0%～5% ，Fe2O30%～3%，K2O 0%～3%。
7. The geopolymer gel material based on copper tailings as claimed in claim 1, wherein the percentage content of each component of the fly ash is SiO2 40%～60%，Al2O3 30%～60%，CaO 0%～10%，MgO 0%～5% ，Fe2O3 0%～3%，K2O 0%～3%。
8. A method for preparing a geopolymer gel material based on copper tailings according to any one of claims 1 to 7, characterized by comprising the following steps:
(1) uniformly mixing the dried, crushed and sieved raw materials according to a ratio to obtain a composite mineral;
(2) mixing Na2SiO3Mixing and stirring water and sodium hydroxide uniformly to prepare an alkali activator solution;
(3) adding an alkali activator solution into the composite mineral, mechanically stirring uniformly, filling into a mold, and pressing and molding at the pressure of 5-8 MPa;
(4) placing the sample and the mold in a curing box, curing for 30-36 h at 50-70 ℃, and then demolding;
(5) and (3) placing the demoulded sample into a constant-temperature constant-humidity curing box, and curing for 3d, 7d and 28d at the temperature of 30-50 ℃ and the humidity of 90-95%.
9. The method for preparing a geopolymer gel material based on copper tailings as claimed in claim 8, wherein the sieving is 200 mesh sieving.
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| CN113998948A (en) * | 2021-11-09 | 2022-02-01 | 中铁隧道局集团有限公司 | Geopolymer-containing cement slurry-based grouting material suitable for high-ground-temperature environment and preparation method thereof |
| CN114105590A (en) * | 2021-12-08 | 2022-03-01 | 昆明理工大学 | Method for fixing arsenic by utilizing tailing-red mud-based geopolymer |
| CN115057640A (en) * | 2022-06-17 | 2022-09-16 | 华东交通大学 | Accelerated excitation method for gelation activity of high-silicon aluminum copper tailings |
| CN115108739A (en) * | 2022-06-24 | 2022-09-27 | 华东交通大学 | Copper tailing geopolymer with high gelling activity and preparation method thereof |
| CN115108739B (en) * | 2022-06-24 | 2023-07-07 | 华东交通大学 | Copper tailing geopolymer with high gelation activity and preparation method thereof |
| CN115124290A (en) * | 2022-07-25 | 2022-09-30 | 昆明理工大学 | Method for fixing copper in wastewater by using fly ash-metakaolin based geopolymer |
| CN115869580A (en) * | 2022-11-29 | 2023-03-31 | 贵州大学 | Mercury tailing curing agent and using method thereof |
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