CN117105549B - Method for preparing magnesium cement cementing material by using industrial waste salt and product thereof - Google Patents
Method for preparing magnesium cement cementing material by using industrial waste salt and product thereof Download PDFInfo
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- CN117105549B CN117105549B CN202311388492.1A CN202311388492A CN117105549B CN 117105549 B CN117105549 B CN 117105549B CN 202311388492 A CN202311388492 A CN 202311388492A CN 117105549 B CN117105549 B CN 117105549B
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 239000011777 magnesium Substances 0.000 title claims abstract description 161
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 161
- 239000004568 cement Substances 0.000 title claims abstract description 134
- 239000000463 material Substances 0.000 title claims abstract description 134
- 150000003839 salts Chemical class 0.000 title claims abstract description 84
- 239000002440 industrial waste Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 87
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000000227 grinding Methods 0.000 claims abstract description 31
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 31
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 31
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 31
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 31
- 239000010881 fly ash Substances 0.000 claims abstract description 30
- 239000002893 slag Substances 0.000 claims abstract description 30
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 29
- 239000010440 gypsum Substances 0.000 claims abstract description 29
- 239000003245 coal Substances 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000003801 milling Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 25
- 238000005260 corrosion Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000001764 infiltration Methods 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 25
- 238000005303 weighing Methods 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- 239000002002 slurry Substances 0.000 description 18
- 239000004576 sand Substances 0.000 description 16
- 229910017053 inorganic salt Inorganic materials 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 9
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical class [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000010998 test method Methods 0.000 description 8
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000391 magnesium silicate Substances 0.000 description 6
- 229910052919 magnesium silicate Inorganic materials 0.000 description 6
- 235000019792 magnesium silicate Nutrition 0.000 description 6
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000011083 cement mortar Substances 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OLZDXDPSDUSGIS-UHFFFAOYSA-N sulfinylmagnesium Chemical compound [Mg].S=O OLZDXDPSDUSGIS-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001653 ettringite Inorganic materials 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920000876 geopolymer Polymers 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- -1 gesso Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000003911 water pollution 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
- C04B9/00—Magnesium cements or similar cements
- C04B9/11—Mixtures thereof with other inorganic cementitious materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B9/00—Magnesium cements or similar cements
- C04B9/20—Manufacture, e.g. preparing the batches
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)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing a magnesium cement cementing material by utilizing industrial waste salt and a product thereof. The method comprises the following steps: mixing industrial waste salt, coal gangue and magnesite, uniformly stirring, grinding into powder, adding water for mixing, stirring, grinding into powder, calcining, and cooling to room temperature to obtain magnesium active coarse material; mixing blast furnace slag and magnesium active coarse material, and grinding to obtain magnesium cement coarse material; mixing the fly ash, the gypsum powder and the magnesium cement coarse material, and uniformly stirring to obtain the magnesium cement cementing material. The preparation process is simple, the efficient recycling of the industrial waste salt is realized through reasonable stirring, salt dissolving, infiltration, drying, calcination and re-proportioning processes, and the prepared magnesium cement cementing material has a uniaxial compressive strength of 56.74MPa at most and a corrosion resistance coefficient of 0.98 at most in 28 days.
Description
Technical Field
The invention relates to a method for preparing a magnesium cement binding material by utilizing industrial waste salt and a product thereof, belonging to the field of resource utilization of dangerous wastes.
Background
The industrial waste salt not only contains soluble inorganic salt, but also contains a plurality of toxic and harmful substances, if the waste salt is randomly disposed and stacked, the waste salt is not only easy to cause serious harm to the ecological environment, but also can directly harm the health of human bodies and induce the canceration of the human bodies. The industrial waste salt has high hygroscopicity and strong water solubility, and the recycling path of the industrial waste salt cannot be expanded due to the strong toxicity of impurity elements contained in the industrial waste salt.
At present, the treatment of industrial waste salt is mainly landfill and incineration. If the industrial waste salt is buried, not only a great deal of land resources are wasted, but also a great deal of high-salt percolate is generated, and serious secondary pollution (such as soil salinization, vegetation wilting and water pollution) is caused to the surrounding environment. Considering the current lack of efficient and viable salt percolation treatment techniques, this places extremely high demands on the landfill facilities and operational management of the industrial waste salts. For incineration disposal, as the heat value of the industrial waste salt is lower and the industrial waste salt is easy to cause corrosion of the hearth of the incinerator in the incineration process, in the actual operation environment, the incineration disposal of the industrial waste salt has higher energy consumption, and a plurality of problems generated in the disposal process are reasonably solved, so that the actual operation working condition is unstable.
The industrial waste salt of different enterprises has individual resource utilization value at present, but the coefficient variation is larger, the comprehensive disposal difficulty is large, and the resource utilization process is long. At present, the disposal of the industrial waste salt mainly aims at purifying and extracting inorganic salt, and the research and the exploration for preparing other resource products by utilizing the industrial waste salt are less. Therefore, if the magnesium cement cementing material can be prepared by utilizing the industrial waste salt, the method not only expands the raw material way for preparing the magnesium cement cementing material, but also provides a beneficial reference for the resource utilization of the industrial waste salt.
The patent application (2022105489269) discloses a method for preparing composite modified magnesium oxychloride cement by utilizing industrial waste salt, which comprises the steps of preparing the magnesium oxychloride cement by the steps (1) and (2), doping the industrial waste salt into the magnesium oxychloride cement by the step (3), curing the industrial waste salt essentially by physical package of the magnesium oxychloride cement, and improving the water resistance of a cured body by permeation of the industrial waste salt in a cement curing body, wherein the method does not relate to the direct reaction process of the industrial waste salt and the magnesium oxychloride cement, and does not relate to the direct preparation of a magnesium oxychloride cement material by taking the industrial waste salt as a raw material. Meanwhile, the invention also needs magnesium chloride and light burned magnesium oxide, and the magnesium cement material cannot be prepared by the reaction of industrial waste salt and other solid wastes.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a method for preparing a magnesium cement cementing material and a product thereof, wherein the method is simple in preparation process and can realize efficient recycling of industrial waste salt.
The technical scheme is as follows: in order to solve the technical problems, the invention provides a method for preparing a magnesium cement gel material by using industrial waste salt, which comprises the following steps:
(1) Mixing industrial waste salt, coal gangue and magnesite, uniformly stirring, and grinding into powder to obtain salt-mixed magnesium gangue powder;
(2) Mixing water with the salt-mixed magnesium gangue powder in the step (1), stirring, grinding into powder, calcining, and cooling to room temperature to obtain magnesium active coarse material;
(3) Mixing blast furnace slag and the magnesium active coarse material in the step (2), and grinding to obtain magnesium cement coarse material;
(4) Mixing the fly ash, the gypsum powder and the magnesium cement coarse material in the step (3), and uniformly stirring to obtain the magnesium cement cementing material.
Wherein, in the step (1), the mass ratio of the industrial waste salt to the coal gangue to the magnesite is 20-40:30-60:100, and the uniaxial compressive strength of the prepared magnesium cement cementing material is more than 42MPa, and the corrosion resistance coefficient is more than or equal to 0.85.
Preferably, in the step (1), the mass ratio of the industrial waste salt to the coal gangue to the magnesite is 20-40:45-60:100, and the uniaxial compressive strength of the prepared magnesium cement cementing material is more than 45MPa, and the corrosion resistance coefficient is more than or equal to 0.85.
Wherein the liquid-solid ratio of the water to the salt mixed magnesium gangue powder in the step (2) is 0.5-1.5:1 mL/g.
Wherein the calcination time in the step (2) is 2-6 hours.
Wherein the calcining temperature in the step (2) is 700-900 ℃.
Wherein the mass ratio of the blast furnace slag to the magnesium active coarse material in the step (3) is 10-30:100, and the uniaxial compressive strength of the prepared magnesium cement cementing material is more than 51MPa, and the corrosion resistance coefficient is more than or equal to 0.92.
Preferably, in the step (3), the mass ratio of the blast furnace slag to the magnesium active coarse material is 20-30:100, the uniaxial compressive strength of the prepared magnesium cement cementing material is more than 53MPa, and the corrosion resistance coefficient is more than or equal to 0.94.
Wherein the grinding time in the step (3) is 1-4 hours.
Wherein the mass ratio of the fly ash to the gypsum powder to the magnesium cement coarse material in the step (4) is 5-15:5-15:100, and the uniaxial compressive strength of the prepared magnesium cement cementing material is more than 52MPa, and the corrosion resistance coefficient is more than or equal to 0.92.
Preferably, in the step (4), the mass ratio of the fly ash to the gypsum powder to the magnesium cement coarse material is 5-15:10-15:100, and the uniaxial compressive strength of the prepared magnesium cement cementing material is more than 54MPa, and the corrosion resistance coefficient is more than or equal to 0.93.
The invention also provides the magnesium cement cementing material prepared by the method.
Reaction mechanism: mixing water and salt with magnesium gangue powder, gradually dissolving waste salt in stirring process, and ionizing to obtain sodium ions, chloride ions, sulfate ions and the like. Sodium ions, chloride ions and sulfate ions permeate into gangue and magnesite powder particles and are adsorbed to the surface of primary minerals. In the calcining process, inorganic salt ions strengthen mineralization and decomposition of organic matters carried by the inorganic salt ions through catalytic decomposition, and high-temperature water vapor and carbon dioxide gas are generated. Under the high-temperature environment, the high Wen Shuiqi and inorganic salt ions adsorbed on the surface of the primary mineral can induce the decomposition and activation of magnesite and coal gangue through the actions of crystal phase activation and lattice doping, and further participate in and induce the decomposition products of the magnesite and the coal gangue to react with the inorganic salt to generate a mixed gel system of magnesium oxychloride cement, magnesium oxysulfide cement, magnesium aluminosilicate cement and magnesium silicate cement. The blast furnace slag and the magnesium active coarse material are mixed to supplement the amorphous silicon source components, strengthen the functions of the magnesium aluminosilicate cement and the magnesium silicate cement and improve the hydration characteristics of the magnesium mixed gel. The fly ash, gypsum powder and magnesium cement coarse material are mixed, and the strength performance and corrosion resistance of the prepared magnesium cement are further improved by adding potential geopolymer reaction and ettringite phase filler to strengthen the compactness of magnesium active gel.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the preparation process is simple, the efficient recycling of the industrial waste salt is realized through reasonable stirring, salt dissolving, infiltration, drying, calcination and re-proportioning processes, and the prepared magnesium cement cementing material has a uniaxial compressive strength of 56.74MPa at most and a corrosion resistance coefficient of 0.98 at most in 28 days.
Drawings
FIG. 1 is a flow chart of the processing method of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Raw material sources and component description: the industrial waste salt is obtained by evaporating medical mother liquor, the medical mother liquor is obtained from Jiangsu Hengrui medical Co., ltd, and the main components of the industrial waste salt are 56.79 percent sodium chloride, 17.85 percent sulfate, 12.37 percent phosphate, 1.15 percent nitrate and other components (organic impurities and loss on ignition); the gangue is from Shanxi mountain coal and electricity Co., ltd, and mainly comprises 46.87% SiO 2 、33.51%Al 2 O 3 、12.04%Fe 2 O 3 、2.72%CaO、2.36K 2 O、1.37%TiO 2 And other components (unavoidable impurities and loss on ignition); magnesite mainly comes from Liaoning Anshan Liaoning Cheng Magnesium group Co., ltd, and mainly comprises 44.38% MgO, 51.39% CO 2 、1.61%CaO、0.86%FeO、0.53%Al 2 O 3 And other components (unavoidable impurities and loss on ignition); fly ash from Taiku power plant of International electric Co Ltd, mainly comprising 43.21% SiO 2 、27.08%Al 2 O 3 、15.62%Fe 2 O 3 、6.58%CaO、3.42%TiO 2 、1.43%SO 3 、1.04%K 2 O、0.63% Na 2 O and other components (unavoidable impurities and loss on ignition); the gypsum powder is from microphone, dihydrate, content 99%, CAS number 10101-41-4, MDL number MFCD00149625; blast furnace slag is from Longteng special steel Co.Ltd, and mainly comprises 42.21% CaO, 37.52% SiO 2 、10.05%Al 2 O 3 、4.62%MgO、2.39%TiO 2 、2.45%SO 3 And other components (unavoidable impurities and loss on ignition).
Example 1 investigation of the Effect of Industrial waste salt, gangue, magnesite Mass ratio on the Performance of magnesium Cement Adhesives
1. Preparation: and respectively weighing industrial waste salt, coal gangue and magnesite according to the mass ratio of 12.5:30:100, 15:30:100, 17.5:30:100, 20:22.5:100, 20:25:100, 20:27.5:100, 20:30:100, 30:30:100, 40:30:100, 20:45:100, 30:45:100, 40:45:100, 20:60:100, 30:60:100, 40:60:100, 40:65:100, 40:70:100, 40:75:100, 45:60:100, 50:60:100 and 55:60:100, uniformly stirring, and grinding into powder to obtain salt-mixed magnesium gangue powder. And (3) mixing water and salt mixed magnesium gangue powder according to a liquid-solid ratio of 0.5:1mL/g, and stirring until the salt mixed magnesium gangue powder is completely dissolved, so as to obtain the salt-penetrated mixed magnesium aluminum slurry. And (3) drying the salt-infiltrated mixed magnesium-aluminum slurry, and grinding the dried salt-infiltrated mixed magnesium-aluminum slurry into powder to obtain salt-infiltrated mixed magnesium-aluminum powder. Calcining the salt-infiltrated mixed magnesium aluminum powder for 2 hours, and cooling to room temperature to obtain magnesium active coarse material, wherein the calcining temperature is 700 ℃. And respectively weighing blast furnace slag and magnesium active coarse material according to the mass ratio of 10:100, mixing, and grinding for 1 hour to obtain magnesium cement coarse material. And respectively weighing the fly ash, the gypsum powder and the magnesium cement coarse material according to the mass ratio of 5:5:100, mixing and stirring uniformly to obtain the magnesium cement cementing material.
2. Performance test: the magnesium cement gel material is prepared into tested gel sand, wherein the blended sand is ISO standard sand specified in the method for testing the strength of cement gel sand (ISO method) GB/T17671-1999, and tap water is selected as water. The preparation of the mortar, the preparation of the test piece, the maintenance of the test piece and the measurement of the compressive strength of the 28d test piece are all carried out according to the GB/T17671-1999 standard of the cement mortar strength test method (ISO method). The test results of this example are shown in Table 1. The measurement and calculation of the corrosion resistance coefficient of the magnesium cement cementing material are according to the test method of cement for sulfate erosion resistance (GB/T749-2008).
TABLE 1 influence of mass ratio of Industrial waste salt, gangue and magnesite on the Performance of Cement gelling Material of magnesium series
| Industrial waste salt, gangue and magnesite mass ratio | Uniaxial compressive Strength (MPa) | Resist factor |
| 12.5:30:100 | 21.91 | 0.63 |
| 15:30:100 | 27.89 | 0.71 |
| 17.5:30:100 | 35.46 | 0.78 |
| 20:22.5:100 | 23.65 | 0.65 |
| 20:25:100 | 28.53 | 0.72 |
| 20:27.5:100 | 34.49 | 0.76 |
| 20:30:100 | 42.37 | 0.85 |
| 30:30:100 | 44.84 | 0.85 |
| 40:30:100 | 46.61 | 0.85 |
| 20:45:100 | 45.92 | 0.86 |
| 30:45:100 | 46.32 | 0.85 |
| 40:45:100 | 48.26 | 0.87 |
| 20:60:100 | 47.14 | 0.88 |
| 30:60:100 | 49.05 | 0.89 |
| 40:60:100 | 49.53 | 0.91 |
| 40:65:100 | 39.68 | 0.82 |
| 40:70:100 | 35.17 | 0.81 |
| 40:75:100 | 30.29 | 0.78 |
| 45:60:100 | 37.81 | 0.80 |
| 50:60:100 | 32.64 | 0.77 |
| 55:60:100 | 28.36 | 0.75 |
As can be seen from table 1, when the mass ratio of the industrial waste salt, the coal gangue, and the magnesite is less than 20:30:100 (as in table 1, the mass ratio of the industrial waste salt, the coal gangue, and the magnesite=17.5:30:100, 15:30:100, 12.5:30:100, 20:27.5:100, 20:25:100, and 20:22.5:100, and the lower ratio not listed in table 1), the addition amount of the industrial waste salt and the coal gangue is small, so that the amount of the mixed gel mixed with the magnesium oxychloride cement, the magnesium oxysulfide cement, the magnesium aluminosilicate cement, and the magnesium silicate cement is reduced, resulting in that the uniaxial compressive strength and the corrosion resistance of the prepared magnesium cement gel material are significantly reduced as the mass ratio of the industrial waste salt, the coal gangue, and the magnesite is reduced. When the mass ratio of the industrial waste salt to the coal gangue to the magnesite is 20-40:30-60:100 (as in table 1, the mass ratio of the industrial waste salt to the coal gangue to the magnesite=20:30:100, 30:30:100, 40:30:100, 20:45:100, 30:45:100, 40:45:100, 20:60:100, 30:60:100, 40:60:100), mixing water and salt with the magnesium gangue powder, gradually dissolving the waste salt during stirring, and ionizing sodium ions, chloride ions, sulfate ions and the like. Sodium ions, chloride ions and sulfate ions permeate into gangue and magnesite powder particles and are adsorbed to the surface of primary minerals. In the calcining process, inorganic salt ions strengthen mineralization and decomposition of organic matters carried by the inorganic salt ions through catalytic decomposition, and high-temperature water vapor and carbon dioxide gas are generated. Under the high-temperature environment, the high Wen Shuiqi and inorganic salt ions adsorbed on the surface of the primary mineral can induce the decomposition and activation of magnesite and coal gangue through the actions of crystal phase activation and lattice doping, and further participate in and induce the decomposition products of the magnesite and the coal gangue to react with the inorganic salt to generate a mixed gel system of magnesium oxychloride cement, magnesium oxysulfide cement, magnesium aluminosilicate cement and magnesium silicate cement. Finally, the uniaxial compressive strength of the prepared magnesium cement binding material is more than 42MPa, and the corrosion resistance coefficient is more than or equal to 0.85. When the mass ratio of the industrial waste salt, the coal gangue and the magnesite is greater than 40:60:100 (as in table 1, the mass ratio of the industrial waste salt, the coal gangue and the magnesite=40:65:100, 40:70:100, 40:75:100, 45:60:100, 50:60:100, 55:60:100 and higher ratio not listed in table 1), the mixing amount of the industrial waste salt and the coal gangue is excessive, the material matching is unbalanced, and the uniaxial compressive strength and the corrosion resistance coefficient of the prepared magnesium cement gel material are obviously reduced as the mass ratio of the industrial waste salt, the coal gangue and the magnesite is further increased.
Therefore, when the mass ratio of the industrial waste salt, the coal gangue and the magnesite is 20-40:30-60:100, the combination of the efficiency and the cost is most favorable for improving the performance of the prepared magnesium cement cementing material.
Example 2 Effect of blast furnace slag and magnesium reactive coarse Mass ratio on magnesium Cement gelling Material Performance
1. Preparation: and respectively weighing industrial waste salt, coal gangue and magnesite according to a mass ratio of 40:60:100, uniformly stirring, and grinding into powder to obtain salt-mixed magnesium gangue powder. Mixing water and salt mixed magnesium gangue powder according to a liquid-solid ratio of 1:1mL/g, and stirring until the salt mixed magnesium gangue powder is completely dissolved, thus obtaining the salt-penetrated mixed magnesium aluminum slurry. And (3) drying the salt-infiltrated mixed magnesium-aluminum slurry, and grinding the dried salt-infiltrated mixed magnesium-aluminum slurry into powder to obtain salt-infiltrated mixed magnesium-aluminum powder. Calcining the salt-infiltrated mixed magnesium aluminum powder for 4 hours, and cooling to room temperature to obtain magnesium active coarse material, wherein the calcining temperature is 800 ℃. And respectively weighing blast furnace slag and magnesium active coarse materials according to the mass ratio of 2.5:100, 5:100, 7.5:100, 10:100, 20:100, 30:100, 35:100, 40:100 and 45:100, mixing, and grinding for 2.5 hours to obtain magnesium cement coarse materials. And respectively weighing the fly ash, the gypsum powder and the magnesium cement coarse material according to the mass ratio of 10:10:100, mixing and stirring uniformly to obtain the magnesium cement cementing material.
2. Performance test: the magnesium cement gel material is prepared into tested gel sand, wherein the blended sand is ISO standard sand specified in the method for testing the strength of cement gel sand (ISO method) GB/T17671-1999, and tap water is selected as water. The preparation of the mortar, the preparation of the test piece, the maintenance of the test piece and the measurement of the compressive strength of the 28d test piece are all carried out according to the GB/T17671-1999 standard of the cement mortar strength test method (ISO method). The test results of this example are shown in Table 2. The measurement and calculation of the corrosion resistance coefficient of the magnesium cement cementing material are according to the test method of cement for sulfate erosion resistance (GB/T749-2008).
TABLE 2 influence of the mass ratio of blast furnace slag to magnesium reactive coarse Material on the Properties of magnesium Cement gelling Material
| Active coarse material mass ratio of blast furnace slag and magnesium | Uniaxial compressive Strength (MPa) | Resist factor |
| 2.5:100 | 29.78 | 0.73 |
| 5:100 | 33.52 | 0.76 |
| 7.5:100 | 40.48 | 0.82 |
| 10:100 | 51.04 | 0.92 |
| 20:100 | 53.25 | 0.94 |
| 30:100 | 54.32 | 0.95 |
| 35:100 | 44.69 | 0.86 |
| 40:100 | 42.53 | 0.83 |
| 45:100 | 36.17 | 0.81 |
As can be seen from table 2, when the mass ratio of the blast furnace slag to the magnesium active coarse material is less than 10:100 (as in table 2, when the mass ratio of the blast furnace slag to the magnesium active coarse material=5:100, 7.5:100, 2.5:100, and lower ratios not listed in table 2), the addition amount of the blast furnace slag is small, the hydration activation function of the magnesium aluminosilicate cement and the magnesium silicate cement is weakened, resulting in that the uniaxial compressive strength and the corrosion resistance of the prepared magnesium cement paste are significantly reduced as the mass ratio of the blast furnace slag to the magnesium active coarse material is reduced. When the mass ratio of the blast furnace slag to the magnesium active coarse material is 10-30:100 (as in table 2, the mass ratio of the blast furnace slag to the magnesium active coarse material=10:100, 20:100 and 30:100), the blast furnace slag and the magnesium active coarse material are mixed to supplement amorphous silicon source components, strengthen the functions of magnesium aluminosilicate cement and magnesium silicate cement and improve the hydration characteristics of magnesium mixed gel. Finally, the uniaxial compressive strength of the prepared magnesium cement binding material is more than 51MPa, and the corrosion resistance coefficient is more than or equal to 0.92. When the mass ratio of the blast furnace slag to the magnesium active coarse material is greater than 30:100 (as in table 2, the mass ratio of the blast furnace slag to the magnesium active coarse material=35:100, 40:100, 45:100, and higher ratios not listed in table 2), the blast furnace slag is excessively doped, the material matching is unbalanced, and the uniaxial compressive strength and the corrosion resistance of the prepared magnesium cement binder are significantly reduced as the mass ratio of the blast furnace slag to the magnesium active coarse material is further increased.
Therefore, when the mass ratio of the blast furnace slag to the magnesium active coarse material is 10-30:100, the magnesium cement cementing material is most beneficial to improving the performance of the prepared magnesium cement cementing material.
EXAMPLE 3 Effect of fly ash, gesso, magnesium Cement coarse Material mass ratio on magnesium Cement gel Material Performance
1. Preparation: and respectively weighing industrial waste salt, coal gangue and magnesite according to a mass ratio of 40:60:100, uniformly stirring, and grinding into powder to obtain salt-mixed magnesium gangue powder. And (3) mixing water and salt mixed magnesium gangue powder according to a liquid-solid ratio of 1.5:1mL/g, and stirring until the salt mixed magnesium gangue powder is completely dissolved, so as to obtain the salt-penetrated mixed magnesium aluminum slurry. And (3) drying the salt-infiltrated mixed magnesium-aluminum slurry, and grinding the dried salt-infiltrated mixed magnesium-aluminum slurry into powder to obtain salt-infiltrated mixed magnesium-aluminum powder. Calcining the salt-infiltrated mixed magnesium aluminum powder for 6 hours, and cooling to room temperature to obtain magnesium active coarse material, wherein the calcining temperature is 900 ℃. And respectively weighing blast furnace slag and magnesium active coarse material according to the mass ratio of 30:100, mixing, and grinding for 4 hours to obtain magnesium cement coarse material. And respectively weighing fly ash, gypsum powder and magnesium cement coarse material according to the mass ratio of 2.5:5:100, 3:5:100, 4:5:100, 5:2.5:100, 5:3:100, 5:4:100, 5:5:100, 10:5:100, 15:5:100, 5:10:100, 10:10:100, 15:15:100, 15:17.5:100, 15:20:100, 15:22.5:100, 17.5:15:100, 20:15:100 and 22.5:15:100, mixing and stirring uniformly to obtain the magnesium cement gel material.
2. Performance test: the magnesium cement gel material is prepared into tested gel sand, wherein the blended sand is ISO standard sand specified in the method for testing the strength of cement gel sand (ISO method) GB/T17671-1999, and tap water is selected as water. The preparation of the mortar, the preparation of the test piece, the maintenance of the test piece and the measurement of the compressive strength of the 28d test piece are all carried out according to the GB/T17671-1999 standard of the cement mortar strength test method (ISO method). The test results of this example are shown in Table 3. The measurement and calculation of the corrosion resistance coefficient of the magnesium cement cementing material are according to the test method of cement for sulfate erosion resistance (GB/T749-2008).
TABLE 3 influence of fly ash, gypsum powder, magnesium cement coarse material mass ratio on magnesium cement gel material performance
| Coarse material mass ratio of fly ash, gypsum powder and magnesium cement | Uniaxial compressive Strength (MPa) | Resist factor |
| 2.5:5:100 | 37.83 | 0.81 |
| 3:5:100 | 40.62 | 0.82 |
| 4:5:100 | 44.76 | 0.84 |
| 5:2.5:100 | 36.87 | 0.81 |
| 5:3:100 | 40.15 | 0.83 |
| 5:4:100 | 43.78 | 0.84 |
| 5:5:100 | 52.36 | 0.92 |
| 10:5:100 | 54.27 | 0.92 |
| 15:5:100 | 55.43 | 0.94 |
| 5:10:100 | 53.89 | 0.93 |
| 10:10:100 | 55.02 | 0.95 |
| 15:10:100 | 56.15 | 0.97 |
| 5:15:100 | 54.68 | 0.96 |
| 10:15:100 | 56.38 | 0.98 |
| 15:15:100 | 56.74 | 0.98 |
| 15:17.5:100 | 51.76 | 0.91 |
| 15:20:100 | 50.21 | 0.91 |
| 15:22.5:100 | 47.93 | 0.88 |
| 17.5:15:100 | 50.46 | 0.90 |
| 20:15:100 | 46.49 | 0.87 |
| 22.5:15:100 | 45.21 | 0.86 |
As can be seen from table 3, when the mass ratio of fly ash, gypsum powder, magnesium-based cement coarse material is less than 5:5:100 (as in table 3, the mass ratio of fly ash, gypsum powder, magnesium-based cement coarse material=4:5:100, 3:5:100, 2.5:5:100, 5:4:100, 5:3:100, 5:2.5:100, and lower ratios not listed in table 3), the addition amounts of fly ash and gypsum powder are smaller, the hydration function of the prepared magnesium-based cement gel material is reduced, resulting in a significant decrease in the uniaxial compressive strength and the corrosion resistance of the prepared magnesium-based cement gel material with a decrease in the mass ratio of fly ash, gypsum powder, magnesium-based cement coarse material. When the mass ratio of the fly ash, the gypsum powder and the magnesium cement coarse material is between 5 and 15:5 and 15:100 (as in table 3, the mass ratio of the fly ash, the gypsum powder and the magnesium cement coarse material=5:5:100, 10:5:100, 15:5:100, 5:10:100, 10:10:100, 15:10:100, 5:15:100, 10:15:100 and 15:15:100), the fly ash, the gypsum powder and the magnesium cement coarse material are mixed, and the strength performance and the corrosion resistance performance of the prepared magnesium cement are further improved by adding the potential geopolymer reaction and the ettringite phase filler to strengthen the density of magnesium active gel. Finally, the uniaxial compressive strength of the prepared magnesium cement binding material is more than 52MPa, and the corrosion resistance coefficient is more than or equal to 0.92. When the mass ratio of fly ash, gypsum powder, magnesium-based cement coarse material is greater than 15:15:100 (as in table 3, the mass ratio of fly ash, gypsum powder, magnesium-based cement coarse material=15:17.5:100, 15:20:100, 15:22.5:100, 17.5:15:100, 20:15:100, 22.5:15:100, and higher ratios not listed in table 3), the fly ash and gypsum powder are excessively mixed, the material matching is unbalanced, resulting in significant decrease of the uniaxial compressive strength and the corrosion resistance of the prepared magnesium-based cement cementing material with further increase of the mass ratio of fly ash, gypsum powder, magnesium-based cement coarse material.
Therefore, when the mass ratio of the fly ash to the gypsum powder to the magnesium cement coarse material is 5-15:5-15:100, the combination of the efficiency and the cost is most favorable for improving the performance of the prepared magnesium cement cementing material.
Comparative examples comparison of the performances of magnesium-based Cement cementing materials prepared by different comparative technologies
1. The preparation method comprises the following steps: and respectively weighing industrial waste salt, coal gangue and magnesite according to a mass ratio of 40:60:100, uniformly stirring, and grinding into powder to obtain salt-mixed magnesium gangue powder. And (3) mixing water and salt mixed magnesium gangue powder according to a liquid-solid ratio of 1.5:1mL/g, and stirring until the salt mixed magnesium gangue powder is completely dissolved, so as to obtain the salt-penetrated mixed magnesium aluminum slurry. And (3) drying the salt-infiltrated mixed magnesium-aluminum slurry, and grinding the dried salt-infiltrated mixed magnesium-aluminum slurry into powder to obtain salt-infiltrated mixed magnesium-aluminum powder. Calcining the salt-infiltrated mixed magnesium aluminum powder for 6 hours, and cooling to room temperature to obtain magnesium active coarse material, wherein the calcining temperature is 900 ℃. And respectively weighing blast furnace slag and magnesium active coarse material according to the mass ratio of 30:100, mixing, and grinding for 4 hours to obtain magnesium cement coarse material. And respectively weighing the fly ash, the gypsum powder and the magnesium cement coarse material according to the mass ratio of 15:15:100, mixing and stirring uniformly to obtain the magnesium cement cementing material.
Comparison Process 1: and respectively weighing industrial waste salt and magnesite according to the mass ratio of 40:100, uniformly stirring, and grinding into powder to obtain salt mixed magnesium powder. Mixing water and salt mixed magnesium powder according to a liquid-solid ratio of 1.5:1mL/g, and stirring until the salt mixed magnesium powder is completely dissolved, thus obtaining the salt-penetrated mixed magnesium slurry. And (3) drying the salt-penetrating mixed magnesium slurry, and grinding the dried salt-penetrating mixed magnesium slurry into powder to obtain salt-penetrating mixed magnesium powder. Calcining the salt-infiltrated mixed magnesium powder for 6 hours, and cooling to room temperature to obtain magnesium active coarse material, wherein the calcining temperature is 900 ℃. And respectively weighing blast furnace slag and magnesium active coarse material according to the mass ratio of 30:100, mixing, and grinding for 4 hours to obtain magnesium cement coarse material. And respectively weighing the fly ash, the gypsum powder and the magnesium cement coarse material according to the mass ratio of 15:15:100, mixing and stirring uniformly to obtain the magnesium cement cementing material.
Comparison process 2: and respectively weighing industrial waste salt and coal gangue according to a mass ratio of 40:60, uniformly stirring, and grinding into powder to obtain salt mixed gangue powder. And (3) mixing water and salt mixed gangue powder according to a liquid-solid ratio of 1.5:1mL/g, and stirring until the salt mixed gangue powder is completely dissolved, so as to obtain the salt-penetrated mixed aluminum paste. And (3) drying the salt-infiltrated mixed aluminum paste, and grinding the dried salt-infiltrated mixed aluminum paste into powder to obtain salt-infiltrated mixed aluminum powder. Calcining the salt-infiltrated mixed aluminum powder for 6 hours, and cooling to room temperature to obtain active coarse material, wherein the calcining temperature is 900 ℃. And respectively weighing blast furnace slag and active coarse materials according to the mass ratio of 30:100, mixing, and grinding for 4 hours to obtain cement coarse materials. And respectively weighing the fly ash, the gypsum powder and the cement coarse material according to the mass ratio of 15:15:100, mixing and stirring uniformly to obtain the cement cementing material.
Contrast process 3: and (3) respectively weighing the coal gangue and the magnesite according to the mass ratio of 60:100, uniformly stirring, and grinding into powder to obtain the magnesium gangue powder. Mixing water and magnesium gangue powder according to a liquid-solid ratio of 1.5:1mL/g, and stirring until the magnesium gangue powder is completely dissolved, thus obtaining mixed magnesium aluminum slurry. And (3) drying the mixed magnesium-aluminum slurry, and grinding the dried mixed magnesium-aluminum slurry into powder to obtain the mixed magnesium-aluminum powder. The mixed magnesium aluminum powder is calcined for 6 hours and cooled to room temperature, thus obtaining magnesium active coarse material, wherein the calcining temperature is 900 ℃. And respectively weighing blast furnace slag and magnesium active coarse material according to the mass ratio of 30:100, mixing, and grinding for 4 hours to obtain magnesium cement coarse material. And respectively weighing the fly ash, the gypsum powder and the magnesium cement coarse material according to the mass ratio of 15:15:100, mixing and stirring uniformly to obtain the magnesium cement cementing material.
2. Performance test: the magnesium cement gel material is prepared into tested gel sand, wherein the blended sand is ISO standard sand specified in the method for testing the strength of cement gel sand (ISO method) GB/T17671-1999, and tap water is selected as water. The preparation of the mortar, the preparation of the test piece, the maintenance of the test piece and the measurement of the compressive strength of the 28d test piece are all carried out according to the GB/T17671-1999 standard of the cement mortar strength test method (ISO method). The test results of this example are shown in Table 4. The measurement and calculation of the corrosion resistance coefficient of the magnesium cement cementing material are according to the test method of cement for sulfate erosion resistance (GB/T749-2008).
Table 4 comparison of the Performance of magnesium cement cements prepared by different comparative techniques
| Type of process | Uniaxial compressive Strength (MPa) | Resist factor |
| The process of the invention | 56.74 | 0.98 |
| Comparative Process 1 | 21.56 | 0.63 |
| Comparative Process 2 | 14.24 | 0.42 |
| Comparative Process 3 | 17.39 | 0.51 |
As can be seen from the results in Table 4, the uniaxial compressive strength and the corrosion resistance coefficient of the American cement cementing materials prepared by the comparative process 1, the comparative process 2 and the comparative process 3 are all significantly lower than those of the process of the invention.
Claims (4)
1. The method for preparing the magnesium cement cementing material by using the industrial waste salt is characterized by comprising the following steps of:
(1) Mixing industrial waste salt, coal gangue and magnesite, uniformly stirring, and grinding into powder to obtain salt-mixed magnesium gangue powder; the mass ratio of the industrial waste salt to the coal gangue to the magnesite is 20-40:30-60:100;
(2) Mixing water with the salt-mixed magnesium gangue powder in the step (1), stirring, grinding into powder, calcining, and cooling to room temperature to obtain magnesium active coarse material; the calcination time is 2-6 hours, and the calcination temperature is 700-900 ℃;
(3) Mixing blast furnace slag and the magnesium active coarse material in the step (2), and grinding to obtain magnesium cement coarse material; the mass ratio of the blast furnace slag to the magnesium active coarse material is 10-30:100;
(4) Mixing the fly ash, the gypsum powder and the magnesium cement coarse material in the step (3), and uniformly stirring to obtain a magnesium cement cementing material; the mass ratio of the fly ash to the gypsum powder to the magnesium cement coarse material is 5-15:5-15:100.
2. The method of claim 1, wherein the liquid-solid ratio of the water and salt mixed magnesium gangue powder in step (2) is 0.5-1.5:1 ml/g.
3. The method of claim 1, wherein the milling in step (3) is performed for a period of 1 to 4 hours.
4. A magnesium cement-based cementitious material prepared by the method of any one of claims 1 to 3.
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