CN115583810A - Double-gel-system composite gel material and preparation and application methods thereof - Google Patents
Double-gel-system composite gel material and preparation and application methods thereof Download PDFInfo
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- CN115583810A CN115583810A CN202211309373.8A CN202211309373A CN115583810A CN 115583810 A CN115583810 A CN 115583810A CN 202211309373 A CN202211309373 A CN 202211309373A CN 115583810 A CN115583810 A CN 115583810A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 41
- 238000000605 extraction Methods 0.000 claims abstract description 39
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 23
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 22
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000292 calcium oxide Substances 0.000 claims abstract description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 14
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 14
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical compound [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229920000876 geopolymer Polymers 0.000 claims abstract description 10
- 238000003483 aging Methods 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000002893 slag Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000404 calcium aluminium silicate Substances 0.000 claims description 3
- 235000012215 calcium aluminium silicate Nutrition 0.000 claims description 3
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 claims description 3
- 229940078583 calcium aluminosilicate Drugs 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- YPSVSPBXPRTRQF-UHFFFAOYSA-N calcium;oxygen(2-);hydrate Chemical class O.[O-2].[Ca+2] YPSVSPBXPRTRQF-UHFFFAOYSA-N 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 230000009977 dual effect Effects 0.000 claims 1
- MJMDTFNVECGTEM-UHFFFAOYSA-L magnesium dichloride monohydrate Chemical class O.[Mg+2].[Cl-].[Cl-] MJMDTFNVECGTEM-UHFFFAOYSA-L 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011398 Portland cement Substances 0.000 abstract 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 14
- 239000004568 cement Substances 0.000 description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005065 mining Methods 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- LRKMVRPMFJFKIN-UHFFFAOYSA-N oxocalcium hydrate Chemical compound [O].O.[Ca] LRKMVRPMFJFKIN-UHFFFAOYSA-N 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 210000004127 vitreous body Anatomy 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B9/00—Magnesium cements or similar cements
- C04B9/20—Manufacture, e.g. preparing the batches
-
- 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
- C04B28/30—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 magnesium cements or similar cements
- C04B28/32—Magnesium oxychloride cements, e.g. Sorel cement
-
- 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
- C04B9/00—Magnesium cements or similar cements
- C04B9/11—Mixtures thereof with other inorganic cementitious materials
- C04B9/12—Mixtures thereof with other inorganic cementitious materials with hydraulic cements, e.g. Portland cements
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention discloses a preparation method of a double-gelling system composite gelling material, which comprises the following steps: adding waste acid and magnesium sulfate into the titanium extraction tailings to obtain a first mixture, and stirring, ageing and drying the first mixture to obtain acidified tailings; and adding magnesium oxide, calcium oxide and sodium silicate into the acidified tailings to obtain a second mixture, and putting the second mixture into a ball mill for ball milling to obtain the double-gel system composite gel material. Wherein the double-gel system comprises a geopolymer gel system and a magnesium oxychloride gel system, and the specific surface area of the composite gel material is more than 400m 2 In terms of/kg. The invention also provides a double-gelling system composite gelling material and an application method thereof. The method has simple steps, no need of portland cement, wide raw material source, low cost and titanium extraction tailingsThe utilization rate reaches more than 80 percent, and the method is applied to the field of mine filling and develops a large-scale utilization way of the titanium extraction tailings.
Description
Technical Field
The invention relates to the technical field of metallurgical solid waste, in particular to a double-gelling-system composite gelling material for mine filling.
Background
The technology for mining and filling the mine simultaneously is a development trend in the future, can ensure the safety and stability of the geology of a mining area, can realize the filling and utilization of tailings, and avoids the stacking of a tailing pond and the influence on the environment. The mine filling cementing material is made of cement at first, most mining enterprises adopt R325 cement to reduce filling cost, and filling requirements can be met, but in recent years, the price of cement rises, and many mining enterprises begin to search for a cementing material with lower cost to replace the cement. Metallurgical slag such as granulated blast furnace slag, steel slag, fly ash, gypsum slag, yellow phosphorus slag and the like has potential gelling performance, and is gradually used as a special mine filling gelling material for replacing cement.
The titanium extraction tailings raw slag in the slag resource has good volcanic ash activity and is ground to 400m of specific surface area 2 More than kg, and the activity index can reach more than 95 percent. Because the titanium chloride extraction process is adopted, the raw slag of the titanium extraction tailings contains higher chlorine, mainly exists in the form of calcium chloride and magnesium chloride, and can not be prepared into slag micro powder to be applied to the cement and concrete industries like common granulated blast furnace slag, so that the application of the titanium extraction tailings in the mine filling field (the requirement of the mine filling field on the chlorine content is not high) needs to be developed. How to prepare the mine filling cementing material by taking the titanium extraction tailings as the raw material is to be further solved.
Therefore, the need exists in the prior art for an improvement in the preparation of mine filling cement materials from titanium extraction tailings.
Disclosure of Invention
In view of the above, the embodiment of the invention aims to provide a double-gelling system composite gelling material and a preparation method thereof.
In view of the above objects, an aspect of the embodiments of the present invention provides a method for preparing a dual-gel system composite gel material, the method comprising the following steps:
adding waste acid and magnesium sulfate into the titanium extraction tailings to obtain a first mixture, and stirring, ageing and drying the first mixture to obtain acidified tailings;
and adding magnesium oxide, calcium oxide and sodium silicate into the acidified tailings to obtain a second mixture, and putting the second mixture into a ball mill for ball milling to obtain the double-gel system composite gel material.
Wherein the double-gel system comprises a geopolymer gel system and a magnesium oxychloride gel system, and the specific surface area of the composite gel material is more than 400m 2 /kg。
In some embodiments, 3% to 5% of waste acid and 1% to 3% of magnesium sulfate are added to the titanium extraction tailings in weight percent to obtain a first mixed material.
In some embodiments, the waste acid is a titanium dioxide-rich waste acid produced by a sulfuric acid process, the acidity is 20%, and the magnesium sulfate is industrially pure with the content of magnesium sulfate being more than 95%.
In some embodiments, 2% to 3% magnesium oxide, 5% to 10% calcium oxide, and 0.5% to 2% sodium silicate are added to the acidified tailings by weight percent to obtain a second blend;
the magnesium oxide is light-burned magnesite powder, wherein the content of the magnesium oxide is more than 90%, the calcium oxide is active lime, wherein the content of the calcium oxide is more than 80%, and the sodium silicate is industrially pure, wherein the content of the sodium silicate is more than 95%.
In some embodiments, the titanium extraction tailings are byproducts of titanium extraction from titanium-containing blast furnace slag after high-temperature carbonization-low-temperature chlorination, and comprise, by weight, 26-30% of calcium oxide, 24-28% of silicon dioxide, 5-10% of titanium dioxide, 12-13% of aluminum oxide, 8-9% of magnesium oxide, 2-4% of chloride ions and 3-5% of free carbon.
In some embodiments, the moisture content of the titanium extraction tailings is 10-15%. In some embodiments, the time of the ageing treatment is 1 to 10 hours.
In some embodiments, the drying process comprises drying and dehydrating at 100-200 ℃ to a water content of less than 1.0%.
The invention also provides a dual-gelling system composite gelling material prepared by the method, which comprises a geopolymer gelling system and a magnesium oxychloride gelling system, wherein the geopolymer gelling system comprises a glassy calcium aluminosilicate substance and calcium oxide hydrate, and the magnesium oxychloride gelling system comprises magnesium oxide and magnesium chloride hydrate.
The invention also provides an application method of the double-gel system composite cementing material, which is characterized in that the double-gel composite cementing material and the tailing ore are uniformly mixed according to the proportion of 1.
The invention has at least the following beneficial technical effects:
the method utilizes the characteristic that the titanium extraction tailings have potential pozzolanic activity, and forms a geopolymer gelling system through mechanical excitation and chemical excitation. The chlorine salt contained in the titanium extraction tailings is utilized to form a magnesium chloride system through treatment, and then a magnesium oxychloride gelling system is formed through introducing magnesium oxide. The method has the advantages of simple steps, no need of silicate cement, wide raw material sources, low cost, utilization rate of the titanium extraction tailings of more than 80 percent, application to the field of mine filling of mining enterprises in the surrounding areas of Shanxi, and development of a large-scale utilization approach of the titanium extraction tailings.
The composite cementitious material and the application method thereof have the same beneficial effects as above.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other embodiments can be obtained by using the drawings without creative efforts.
FIG. 1 is a schematic diagram of an embodiment of a method for preparing a dual-gel system composite gel material provided by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments of the present invention are described in further detail with reference to the accompanying drawings.
The terms "including" and "having," and any variations thereof in the description and claims of this invention and the description of the figures above, are intended to cover non-exclusive inclusions; the terms "first," "second," and the like in the description and claims of the present invention or in the foregoing drawings are used for distinguishing between different objects and not for describing a particular sequential order. The meaning of "plurality" is two or more unless specifically limited otherwise.
Furthermore, reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the invention. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
FIG. 1 is a schematic diagram showing an embodiment of a method for preparing a dual-gel system composite gel material, wherein the method comprises the following steps:
(1) Adding waste acid (sulfuric acid process titanium dioxide byproduct waste sulfuric acid, the acidity is about 20%) and magnesium sulfate (industrial purity, the content of magnesium sulfate is more than 95%) into the titanium extraction tailings to obtain a first mixture, and stirring, ageing and drying the first mixture to obtain acidified tailings;
(2) Adding magnesium oxide (light-burned magnesite powder, the content of magnesium oxide is more than 90%), calcium oxide (active lime, the content of calcium oxide is more than 80%) and sodium silicate (industrial pure, the content of sodium silicate is more than 95%) into the acidified tailings to obtain a second mixture, and putting the second mixture into a ball mill for ball milling to obtain the double-gel system composite gel material.
Wherein the double-gel system comprises a geopolymer gel system and a magnesium oxychloride gel system, and the specific surface area of the composite gel material is more than 400m 2 /kg。
Furthermore, the titanium extraction tailings used in the invention are byproducts of titanium extraction from titanium-containing blast furnace slag through high-temperature carbonization and low-temperature chlorination, the titanium extraction tailings comprise, by weight, 26-30% of calcium oxide, 24-28% of silicon dioxide, 5-10% of titanium dioxide, 12-13% of aluminum oxide, 8-9% of magnesium oxide, 2-4% of chloride ions and 3-5%, the titanium extraction tailings are subjected to heat treatment at 600-700 ℃ to remove free carbon therein, and other components are retained, and the water content of the titanium extraction tailings is 10-15%.
Further, in the step (1), 3% -5% of waste acid and 1% -3% of magnesium sulfate are added into the titanium extraction tailings to obtain a first mixture, the first mixture is subjected to dispersion stirring treatment, ageing is carried out for 1-10 hours, and then drying and dewatering are carried out at the temperature of 100-200 ℃ until the water content is below 1.0% so as to obtain the acidified tailings.
Further, in the step (2), 2% -3% of magnesium oxide, 5% -10% of calcium oxide and 0.5% -2% of sodium silicate are added into the acidified tailings to obtain a second mixture, the second mixture is added into a ball mill for mixing and ball milling, and the specific surface area is controlled to be 400m 2 Kg, to obtain the double-gelling system composite gelling material.
The method of the invention respectively carries out acidification treatment and magnesium treatment on the titanium extraction tailings to form a composite gelled material; the potential activity of the vitreous body in the titanium extraction tailings can be further released through acidification treatment, and the volcanic ash activity of the titanium extraction tailings can be improved; meanwhile, a small amount of free chlorine in the titanium extraction tailings is further reacted into chloride ions, which is beneficial to the subsequent formation of magnesium chloride; magnesium sulfate is introduced through magnesium treatment, so that calcium chloride in the titanium extraction tailings is converted into calcium sulfate and magnesium chloride, the content of magnesium chloride in the titanium extraction tailings is increased, and the formed calcium sulfate is in a long and thin fiber shape and can play a role in reinforcement.
The invention also provides a composite cementing material of a double-cementing system prepared by the method,the double-gel system composite cementing material comprises a geopolymer cementing system and a magnesium oxychloride cementing system, wherein the geopolymer cementing system comprises more than 90% of vitreous state calcium aluminosilicate substances, has potential pozzolanic activity, can form C-S-H cement stone through alkali excitation of calcium oxide, sodium silicate and the like, and plays a role in improving the strength of a matrix; the magnesium oxychloride gel system comprises hydrates of magnesium oxide and magnesium chloride, magnesium chloride formed after the magnesium treatment of titanium extraction tailings is fully utilized, magnesium oxide is added to form the magnesium oxychloride gel system, and 318 (3 MgO-MgCl) is formed through hydration reaction 2 -8H 2 O) and 518 (5 MgO-MgCl) 2 -8H 2 O) hydrate, which plays a role in improving the strength of the matrix.
The invention also provides an application method of the double-gelling system composite gelling material, which is characterized in that the prepared composite gelling material and the tailing ore are uniformly mixed according to the proportion of 1.
The following further illustrates embodiments of the invention in terms of specific examples.
Example 1
Firstly, 3-5% of waste acid (acidity is about 20%) and 1-3% of magnesium sulfate (industrial purity is more than or equal to 95%) are mixed into titanium extraction tailings with the water content of 10-15%, and then the titanium extraction tailings are subjected to dispersion stirring treatment, and the mixture is aged for 1-10 hours to ensure that the mixture is fully reacted and stabilized. Then drying and dehydrating at 100-200 ℃ until the water content is below 1.0%. Adding 2-3% of magnesium oxide (magnesium oxide powder with effective component more than or equal to 90%), 5-10% of calcium oxide (lime powder with effective component more than or equal to 80%) and 0.5-2% of sodium silicate (industrial purity more than or equal to 95%) into the dried acidified tailings, mixing and ball-milling by adopting a ball mill, and controlling the specific surface area to be 400m 2 And/kg or more, and preparing the double-gel system composite gel material for filling the mine.
The main indexes are as follows: density: 1.1.50-1.55 g/cm 3 Specific surface area: not less than 400m 2 Kg, compressive strength: the 7d strength is more than or equal to 3MPa, and the 28d strength is more than or equal to 6MPa.
The application comprises the following steps: the composite cementing material is mixed with tailing sand for use, the ash-material ratio (the ratio of the cementing material to the tailing sand) is 1-5-1, the slurry concentration is 70-75%, the 7d strength is more than or equal to 1.5MPa, and the expansion degree and the sedimentation performance both meet the pumping requirements.
The foregoing is an exemplary embodiment of the present disclosure, but it should be noted that various changes and modifications could be made herein without departing from the scope of the present disclosure as defined by the appended claims. The functions, steps and/or actions of the method claims in accordance with the disclosed embodiments described herein need not be performed in any particular order. Furthermore, although elements of the embodiments of the invention may be described or claimed in the singular, the plural is contemplated unless limitation to the singular is explicitly stated.
It should be understood that, as used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly supports the exception. It should also be understood that "and/or" as used herein is meant to include any and all possible combinations of one or more of the associated listed items.
The numbers of the embodiments disclosed in the embodiments of the present invention are merely for description, and do not represent the merits of the embodiments.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, of embodiments of the invention is limited to these examples; within the idea of an embodiment of the invention, also combinations between technical features in the above embodiments or in different embodiments are possible, and there are many other variations of the different aspects of the embodiments of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of the embodiments of the present invention are intended to be included within the scope of the embodiments of the present invention.
Claims (10)
1. A preparation method of a double-gelling system composite gelling material is characterized by comprising the following steps:
adding waste acid and magnesium sulfate into the titanium extraction tailings to obtain a first mixture, and stirring, ageing and drying the first mixture to obtain acidified tailings;
adding magnesium oxide, calcium oxide and sodium silicate into the acidified tailings to obtain a second mixture, and putting the second mixture into a ball mill for ball milling to obtain a double-gel system composite cementing material;
wherein the double-gelling system comprises a geopolymer gelling system and a magnesium oxychloride gelling system, and the specific surface area of the composite gelling material is more than 400m 2 /kg。
2. The preparation method of the double-gelling system composite cementitious material according to claim 1, characterized in that 3-5% of the waste acid is added to the titanium extraction tailings, and 1-3% of the magnesium sulfate is added to obtain the first mixture.
3. The preparation method of the double-gelling system composite gelling material of claim 2, wherein said waste acid is a sulfate process titanium dioxide-rich waste acid, the acidity is 20%, and said magnesium sulfate is in industrial purity with a magnesium sulfate content of more than 95%.
4. The preparation method of the double-gelling system composite cementitious material according to claim 1, characterized by adding 2-3% of the magnesium oxide, 5-10% of the calcium oxide and 0.5-2% of the sodium silicate to the acidified tailings in weight percentage to obtain the second mixture;
the magnesium oxide is light-burned magnesia powder, wherein the content of magnesium oxide is more than 90%, the calcium oxide is active lime, wherein the content of calcium oxide is more than 80%, and the sodium silicate is industrial pure, wherein the content of sodium silicate is more than 95%.
5. The preparation method of the double-gelling system composite cementitious material of claim 1, wherein the titanium extraction tailings are byproducts of titanium-containing blast furnace slag after high-temperature carbonization-low-temperature chlorination titanium extraction, and comprise, by weight, 26-30% of calcium oxide, 24-28% of silicon dioxide, 5-10% of titanium dioxide, 12-13% of aluminum oxide, 8-9% of magnesium oxide, 2-4% of chloride ions, and 3-5% of free carbon.
6. The preparation method of the double-gelling system composite gelling material of claim 1, wherein the moisture content of the titanium extraction tailings is 10-15%.
7. The preparation method of the dual-gelling system composite gelling material of claim 1, wherein the ageing treatment time is 1-10 h.
8. The method for preparing the dual-gelling system composite gelling material of claim 1, wherein the drying treatment comprises drying dehydration at 100-200 ℃ until the water content is less than 1.0%.
9. A dual cementitious system composite cementitious material prepared using the method claimed in any preceding claim, comprising a geopolymer cementitious system comprising glassy calcium aluminosilicate material and calcium oxide hydrates and a magnesium oxychloride cementitious system comprising magnesium oxide and magnesium chloride hydrates.
10. The application method of the dual-gelling system composite cementitious material according to claim 9, wherein the dual-gelling system composite cementitious material is uniformly mixed with the tailings in a ratio of 1.
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