CN109503009B - Modified magnesium sulfate cement and preparation method thereof - Google Patents
Modified magnesium sulfate cement and preparation method thereof Download PDFInfo
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- CN109503009B CN109503009B CN201811491584.1A CN201811491584A CN109503009B CN 109503009 B CN109503009 B CN 109503009B CN 201811491584 A CN201811491584 A CN 201811491584A CN 109503009 B CN109503009 B CN 109503009B
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- 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
- C04B9/04—Magnesium cements containing sulfates, nitrates, phosphates or fluorides
Abstract
The invention provides a preparation method of modified magnesium sulfate cement, which comprises the following steps: (1) weighing concentrated sulfuric acid, ultrafine fly ash, magnesium oxide and water according to a certain proportion for later use; (2) adding concentrated sulfuric acid into a certain amount of standby water to prepare a dilute sulfuric acid solution, then adding the ultrafine fly ash, and stirring to obtain activated modified ultrafine fly ash; (3) slowly adding 10-20% of standby magnesium oxide into the mixture obtained in the step (2), adjusting and stirring to fully dissolve active magnesium oxide, and obtaining a mixture of fly ash and magnesium sulfate solution; (4) and (3) weighing a certain amount of additive (adding the additive into the residual water, stirring and dissolving at room temperature, adding the mixture obtained in the step (3), continuously adding the residual magnesium oxide, and stirring for 30-60 min to obtain the viscous magnesium sulfate cement paste, wherein the compressive strength of the magnesium sulfate cement obtained by the invention can reach 66.96MPa in 28 days, and the method is simple to operate, low in cost and easy to realize industrialization.
Description
Technical Field
The invention relates to magnesium sulfate cement and a preparation method thereof, in particular to modified magnesium sulfate cement taking activated modified ultrafine fly ash as a filler and a preparation method thereof.
Background
The magnesium-based cement has the advantages of quick setting, high strength, wear resistance and the like, is an important supplement of ordinary silicon cement, and has the advantages of improving the functions of building materials, saving energy, protecting environment, and greatly developing CO2The method has important significance in emission reduction, magnesium resource recycling and the like. The magnesium-based cement mainly comprises phosphorus-oxygen-magnesium cement, magnesium oxychloride cement and magnesium oxysulfate cement, wherein the magnesium oxysulfate cement has the advantages of light weight, quick setting, early strength, wear resistance and the like similar to the phosphorus-oxygen-magnesium cement and the magnesium oxychloride cement, but does not have the defects of halogen return and moisture absorption, poor water resistance, strong corrosivity of chloride ions to reinforcing steel bars and the like of the magnesium oxychloride cement, and is the magnesium cement which is most likely to be applied in a large scale. However, the mechanical properties of magnesium oxysulfate cement are poor, and the actual requirements are difficult to meet.
The fly ash is a large amount of industrial solid waste generated by coal-fired power plants, and is a mineral admixture widely applied to portland cement due to the volcanic ash property of the fly ash. In recent years, fly ash has also been reported as a filler in the preparation of magnesium-based cementitious materials. For example, patent CN106747240A proposes an alkaline magnesium oxysulfate cement and a preparation method thereof, wherein the raw materials mainly comprise light-burned magnesium oxide, magnesium sulfate heptahydrate as a byproduct of magnesium desulfurization and fly ash, and due to the adoption of inorganic and organic combined additives, the formation of insoluble whiskers is facilitated, and various properties of the magnesium oxysulfate cement are improved. The prepared test block has the highest compression strength of 67.9-72.5 MPa in 28 days, the flexural strength of 19.5 MPa and the softening coefficient of 0.88-0.95 in 120 days.
The patent CN106554160A proposes a method for directly preparing rapid-setting magnesium oxysulfate cement by using waste sulfuric acid with the concentration of 45-50%, so that the treatment of industrial waste sulfuric acid is solved, the preparation links of magnesium sulfate and a solution thereof are reduced, the production cost of the magnesium oxysulfate cement is reduced, the 28-day compressive strength of the prepared cement is 32.3-65.3 MPa, and the flexural strength is 3.2-12.6 MPa. The patent CN107473614A discloses a water-resistant high-folding-resistance magnesium oxysulfate inorganic cementing material and a preparation method thereof, due to the fact that high-quality fly ash (containing 70% of spherical glass bodies) is doped, hydration heat and drying shrinkage of the cementing material are reduced, performances such as impermeability, frost resistance, elastic modulus, mechanics and the like are effectively improved, folding strength of 28 days of age reaches 22-23 MPa, a prepared standard mortar test piece has high water resistance, the softening coefficient reaches about 0.90, and the cementing material is suitable for important structures which are soaked in water or are in a humid environment. In the preparation method of the modified magnesium oxysulfate cement disclosed in patent CN102924038A, when formic acid and formate are used as additives and fly ash is used as filler, the obtained cement test block has compressive strengths of 69 MPa and 73 MPa respectively, has excellent mechanical properties, and can be used for producing materials such as mortar, concrete, plates, artware and the like instead of magnesium oxychloride cement.
However, in the preparation method reported in the above document, fly ash is only a common mineral filler in the magnesium-based cementing material, and the performance improvement of the cementing material is limited to compact filling, and the mechanism of action of the components such as surface active aluminum and silicon in the cementing material is not clear. In order to further strengthen the action mechanism of the fly ash in the magnesium-based cementing material and improve various properties of magnesium sulfate cement, development of a new preparation method and a new process route are urgently needed.
Disclosure of Invention
The invention aims to solve the problem of a preparation method of modified magnesium sulfate cement and provides a preparation method of modified magnesium sulfate cement.
The technical scheme of the method is that the preparation method of the modified magnesium sulfate cement comprises the following steps:
(1) weighing a certain amount of concentrated sulfuric acid, ultrafine fly ash, magnesium oxide and water for later use according to the mass ratio of the concentrated sulfuric acid to the ultrafine fly ash to the active magnesium oxide to the water of 1: 0.42-1.64: 1.72-3.86: 3.48-4.75;
(2) adding concentrated sulfuric acid into a certain amount of standby water to prepare a 10-30% dilute sulfuric acid solution, then adding ultrafine fly ash, and stirring for 1-5 hours at room temperature to obtain activated modified ultrafine fly ash;
(3) gradually adding 10-20% of standby magnesium oxide into the mixture obtained in the step (2), stirring while adding, adjusting the stirring speed to be 100-500 r/min, stirring for 0.5-2 h, and continuously stirring for 10-30 min after adding to fully dissolve the active magnesium oxide to obtain a mixture of fly ash and magnesium sulfate solution;
(4) weighing a certain amount of the additive according to the mass ratio of the additive to the active magnesium oxide of 0.5-2: 100, adding the additive into the residual water, stirring and dissolving at room temperature, adding the mixture into the mixture obtained in the step (3), stirring for 5-10 min, fully mixing, continuously adding the residual magnesium oxide, and stirring for 30-60 min to obtain viscous magnesium sulfate cement paste;
(5) pouring the cement paste obtained in the step (4) into a standard stainless steel three-connection die (40 multiplied by 40 mm), placing the standard stainless steel three-connection die on a cement mortar vibrating table, vibrating for 60 s, leveling, curing the test piece for one day at room temperature, then demoulding, and continuing curing at room temperature until the test age.
The additive is one of the following substances: citric acid and citrate, tartaric acid and tartrate, phosphoric acid and phosphate, sucrose, glucose, etc.)
Preferably, in the step (1), the concentration of the dilute sulfuric acid solution is 20-25%, the dilute sulfuric acid can be industrial waste sulfuric acid,
preferably, in the step (1), the particle size of the ultrafine fly ash is 1-5 μm.
Preferably, in the step (1), the mass ratio of the concentrated sulfuric acid to the ultrafine fly ash to the active magnesium oxide to the water is 1: 0.42-1.64: 2.15-3.43: 3.48-4.75.
Preferably, in the step (2), the addition amount of magnesium oxide is controlled to 15%.
Preferably, in the step (3), the additive is preferably citric acid or sodium citrate.
Compared with the prior art, the invention has the advantages and effects that: (1) the invention takes dilute sulphuric acid solution as a reaction medium, adopts a one-pot method, and directly completes the activation modification of fly ash, the preparation of magnesium sulfate solution and the preparation of magnesium sulfate cementing material in a reaction kettle in sequence. Firstly, a dilute sulfuric acid solution is used as a fly ash activation modifier, the surface of the fly ash is etched and activated at normal temperature, so that soluble aluminum and amorphous silicon on the surface enter the solution, the surface appearance is porous, and active sites are increased; secondly, in the process, part (but not all) of magnesium oxide is added into the mixture of sulfuric acid and fly ash to prepare a magnesium sulfate solution, and then the rest magnesium oxide is gradually added after the additive is added, so that the generation of a 517 phase is facilitated, and the generation of magnesium hydroxide is reduced. (2) The fly ash selected by the invention is ultrafine powder, the particle size distribution is about 1-10 mu m, and micron-sized ultrafine fly ash particles can be obtained on one hand by supersonic steam grinding, so that the surface energy is remarkably increased, and the volcanic ash characteristics are fully exerted; on the other hand, the fly ash particles are ultra-fine, which is beneficial to improving the surface etching activation degree and increasing the surface area, and the adhesive connection effect between 517-phase gel and the fly ash particles is strengthened, so that the compressive strength of the magnesium sulfate cement is improved. (3) The soluble aluminum and the amorphous silicon entering the solution can further generate hydration reaction with magnesium ions (as shown in the reactions (1) and (2)) to generate insoluble aluminum (silicon) magnesium gelled products, so that a fine pore structure is formed, and the compressive strength of the cement is further improved.
The principle of the invention is as follows:
drawings
FIG. 1 shows the contents of Al, Fe and Ca in the filtrates obtained by activating ultrafine fly ash with sulfuric acid at different concentrations in example 1.
FIG. 2 is SEM images of ultra-fine fly ash (a) and sulfuric acid activated fly ash of example 1 with different concentrations of (b)10% dilute sulfuric acid, (c)20% dilute sulfuric acid, and (d)30% dilute sulfuric acid.
FIG. 3 shows XRD patterns of ultrafine fly ash (a) and sulfuric acid activated fly ash of different concentrations in example 1, (b)10% dilute sulfuric acid, (c)20% dilute sulfuric acid, and (d)30% dilute sulfuric acid.
FIG. 4 is an SEM image of magnesium sulfate cement obtained in examples 2, 3 and 4 and comparative example 5: (a) 10% of activated fly ash is doped in the activated fly ash, (b) 20% of activated fly ash is doped in the activated fly ash, (c) 30% of activated fly ash is doped in the activated fly ash, and (d) no fly ash is doped in the activated fly ash.
FIG. 5 is an XRD pattern of magnesium sulfate cement obtained in examples 2, 3, 4 and comparative example 5: (a) 10% of activated fly ash is doped in the activated fly ash, (b) 20% of activated fly ash is doped in the activated fly ash, (c) 30% of activated fly ash is doped in the activated fly ash, and (d) no fly ash is doped in the activated fly ash.
As is clear from FIG. 1, the amount of aluminum and iron eluted gradually increases and the amount of calcium eluted decreases as the concentration of dilute sulfuric acid increases, and the aluminum content in the solution becomes 2 g/L or more at a dilute sulfuric acid concentration of 20%.
As can be seen from FIG. 2, when the concentration of dilute sulfuric acid is 20%, the ultrafine fly ash surface is largely cellular.
It can be seen from fig. 3 that the diffraction peak of CaSO4 in the modified fly ash gradually increased with increasing concentration of dilute sulfuric acid.
As can be seen from fig. 4, when no fly ash is blended, a needle-like 517-phase crystal is obtained; when the doping amount is 10%, the crystal is thinner and shorter, but is more compact; when the content is 20%, the crystal is lengthened and thinned; the strength of the corresponding test block is increased from 43.16MPa to 66.96MPa, but when the content reaches 30%, the test block becomes flocculent fine crystals, and the strength of the test block is reduced to 49.88 MPa.
As can be seen from fig. 5, the peak intensity of the 517 phase gradually decreased with increasing incorporation of the activated fly ash.
Detailed Description
The invention will be further elucidated with reference to the embodiments and the drawings.
Experimental example 1
Weighing three parts of 10 g of ultrafine fly ash (1-5 mu m), respectively adding the three parts into 100 mL of 10%, 20% and 30% dilute sulfuric acid solution, stirring for 2h at room temperature, and filtering for separation. ICP is adopted to measure aluminum, iron and calcium in the filtrate, and the result is shown in figure 1; washing the obtained solid powder to be neutral by using deionized water, drying the powder for 3-5 h at 105 ℃, and then characterizing by adopting SEM and XRD, wherein the results are shown in figures 2 and 3; the specific surface area of the solution was measured by low-temperature nitrogen adsorption and found to be 19, 48 and 28 m, respectively2/g。
Example 1
(1) 58.80g of concentrated sulfuric acid, 24.96g of ultrafine fly ash, 126.05g of magnesium oxide and 217.26g of water are weighed according to the mass ratio of 1:0.42:2.15:3.69 of concentrated sulfuric acid, ultrafine fly ash (1-5 microns), active magnesium oxide and water for later use, (2) the concentrated sulfuric acid is added into 204.63g of the later-used water to prepare a 20% dilute sulfuric acid solution, then the ultrafine fly ash is added, and the mixture is stirred for 2 hours at room temperature to obtain activated modified ultrafine fly ash; (3) slowly adding 18.91g of standby magnesium oxide into the mixture obtained in the step (2), adjusting the stirring speed to 400 r/min, stirring for 1.5 h, and continuing stirring for 15 min after the addition is finished so as to fully dissolve the active magnesium oxide, thereby obtaining a mixture of fly ash and magnesium sulfate solution; (4) weighing 1.26g of citric acid into the residual water according to the mass ratio of the additive to the active magnesium oxide of 1:100, stirring and dissolving at room temperature, adding into the mixture obtained in the step (3), stirring for 10 min, fully mixing, continuously adding the residual magnesium oxide, and stirring for 30min to obtain viscous magnesium sulfate cement paste; (5) pouring the cement paste obtained in the step (4) into a standard stainless steel three-link mold (40 multiplied by 40 mm), placing the mold on a cement mortar vibrating table, vibrating for 60 s, leveling, curing the test piece for one day at room temperature, demolding, continuing curing for 28 days at room temperature to obtain the compressive strength of the magnesium sulfate cement test block of 53.39 MPa, and performing SEM and XRD characterization on the test block, wherein the SEM and XRD characterization are shown in a figure 4(a) and a figure 5 (a).
Example 2
(1) 58.80g of concentrated sulfuric acid, 56.19g of ultrafine fly ash, 151.26g of magnesium oxide and 244.44g of water are weighed according to the mass ratio of 1:0.95:2.58:4.16 of concentrated sulfuric acid, ultrafine fly ash (1-5 microns), active magnesium oxide and water for later use, (2) the concentrated sulfuric acid is added into 204.63g of the later-used water to prepare a 20% dilute sulfuric acid solution, then the ultrafine fly ash is added, and the mixture is stirred for 2 hours at room temperature to obtain activated modified ultrafine fly ash; 3) slowly adding 22.69g of standby magnesium oxide with the concentration of 15% into the mixture obtained in the step (2), adjusting the stirring speed to 400 r/min, stirring for 1.5 h, and continuing stirring for 15 min after the addition is finished so as to fully dissolve the active magnesium oxide, thereby obtaining a mixture of fly ash and magnesium sulfate solution; (4) weighing 1.51g of citric acid into the residual water according to the mass ratio of the additive to the active magnesium oxide of 1:100, stirring and dissolving at room temperature, adding into the mixture obtained in the step (3), stirring for 10 min, fully mixing, continuously adding the residual magnesium oxide, and stirring for 30min to obtain viscous magnesium sulfate cement paste; (5) pouring the cement paste obtained in the step (4) into a standard stainless steel three-connection die (40 multiplied by 40 mm), placing the standard stainless steel three-connection die on a cement mortar compaction table, vibrating for 60 s, leveling, curing the test piece for one day at room temperature, then demoulding, and continuing curing for 28 days at room temperature. The compressive strength of the magnesium sulfate cement test block is 66.96MPa, and the test block is subjected to SEM and XRD characterization, and is shown in figure 4(b) and figure 5 (b).
Example 3
(1) 58.80g of concentrated sulfuric acid, 96.33g of ultrafine fly ash, 201.68g of magnesium oxide and 279.33g of water are weighed according to the mass ratio of 1:1.64:3.43:4.75 of concentrated sulfuric acid to 1-5 μm of ultrafine fly ash, active magnesium oxide and water for later use, (2) the concentrated sulfuric acid is added into 204.63g of the later-used water to prepare a 20% dilute sulfuric acid solution, then the ultrafine fly ash is added, and the mixture is stirred for 2 hours at room temperature to obtain activated modified ultrafine fly ash; 3) slowly adding 30.25g of standby magnesium oxide accounting for 15% of the weight of the fly ash into the mixture obtained in the step (2), adjusting the stirring speed to 400 r/min, stirring for 1.5 h, and continuing stirring for 15 min after the addition is finished so as to fully dissolve the active magnesium oxide, thereby obtaining a mixture of the fly ash and the magnesium sulfate solution; (4) weighing 2.02g of citric acid into the residual water according to the mass ratio of the additive to the active magnesium oxide of 1:100, stirring and dissolving at room temperature, adding into the mixture obtained in the step (3), stirring for 10 min, fully mixing, continuously adding the residual magnesium oxide, and stirring for 30min to obtain viscous magnesium sulfate cement paste; (5) pouring the cement paste obtained in the step (4) into a standard stainless steel three-connection die (40 multiplied by 40 mm), placing the standard stainless steel three-connection die on a cement mortar compaction table, vibrating for 60 s, leveling, curing the test piece for one day at room temperature, then demoulding, and continuing curing for 28 days at room temperature. The compressive strength of the magnesium sulfate cement test block is 49.88MPa, and the test block is characterized by SEM and XRD, which is shown in figure 4(c) and figure 5 (c).
Comparative example 4
(1) 58.80g of concentrated sulfuric acid, 151.26g of magnesium oxide and 204.63g of water are weighed according to the mass ratio of 1:2.58:3.48 of the concentrated sulfuric acid, the active magnesium oxide and the water for later use; (2) adding concentrated sulfuric acid into 204.63g of standby water to prepare a 20% dilute sulfuric acid solution, slowly adding 22.69g of standby magnesium oxide into the mixture obtained in the step (1), adjusting the stirring speed to 400 r/min, stirring for 1.5 h, and continuing stirring for 15 min after the addition is finished to fully dissolve the active magnesium oxide to obtain a mixture of fly ash and magnesium sulfate solution; (3) weighing 1.51g of citric acid according to the mass ratio of the additive to the active magnesium oxide of 1:100, adding the citric acid into the mixture obtained in the step (2), stirring for 10 min, fully mixing, continuously adding the rest magnesium oxide, and stirring for 30min to obtain viscous magnesium sulfate cement paste; (5) pouring the cement paste obtained in the step (4) into a standard stainless steel three-connection die (40 multiplied by 40 mm), placing the standard stainless steel three-connection die on a cement mortar compaction table, vibrating for 60 s, leveling, curing the test piece for one day at room temperature, then demoulding, and continuing curing for 28 days at room temperature. The compression strength of the magnesium sulfate cement without the fly ash is 43.16MPa, and SEM and XRD characterization is carried out on the test block, and the test block is shown in figure 4(d) and figure 5 (d).
Claims (7)
1. The preparation method of the modified magnesium sulfate cement is characterized by comprising the following steps:
(1) weighing a certain amount of concentrated sulfuric acid, ultrafine fly ash, magnesium oxide and water for later use according to the mass ratio of 1: 0.42-1.64: 1.72-3.86: 3.48-4.75 of the concentrated sulfuric acid, the ultrafine fly ash, the active magnesium oxide and the water;
(2) adding concentrated sulfuric acid into a part of standby water to prepare a 10-30% dilute sulfuric acid solution, then adding ultrafine fly ash, and stirring for 1-5 hours at room temperature to obtain an activated and modified ultrafine fly ash dilute sulfuric acid mixture;
(3) gradually adding 10-20% of standby magnesium oxide into the mixture obtained in the step (2), continuously stirring while adding, adjusting the stirring speed to be 100-500 r/min, stirring for 0.5-2 h, and continuously stirring for 10-30 min after adding to fully dissolve the active magnesium oxide to obtain a mixture of fly ash and magnesium sulfate solution;
(4) weighing a certain amount of the additive according to the mass ratio of the additive to the active magnesium oxide of 0.5-2: 100, adding the additive into the rest of the standby water, stirring and dissolving at room temperature, adding the mixture obtained in the step (3), stirring for 5-10 min, fully mixing, continuously adding the rest of magnesium oxide, and stirring for 30-60 min to obtain viscous magnesium sulfate cement paste;
(5) pouring the cement paste obtained in the step (4) into a standard 40X 40 mm stainless steel triple-link mold, placing the mold on a cement mortar vibrating table, vibrating for 60 s, leveling, curing the test piece for one day at room temperature, demolding, and continuing curing at room temperature until the test age.
2. The method of preparing a modified magnesium sulfate cement as claimed in claim 1, wherein:
the fly ash in the step (1) is ultrafine fly ash prepared by a supersonic steam pulverizer, and the particle size range of the fly ash is 1-10 mu m.
3. The method of preparing a modified magnesium sulfate cement as claimed in claim 1, wherein:
the active magnesium oxide in the step (1) is prepared by direct pyrolysis of bischofite in Qinghai salt lake after recrystallization, or is prepared by a brine method, or is prepared by calcining magnesite.
4. The method of preparing a modified magnesium sulfate cement as claimed in claim 1, wherein: the additive is one of citric acid, citrate, tartaric acid and tartrate, phosphoric acid and phosphate, sucrose and glucose.
5. The method of preparing a modified magnesium sulfate cement as claimed in claim 2, wherein: in the step (1), the particle size of the ultrafine fly ash is 1-5 μm.
6. The method of preparing a modified magnesium sulfate cement as claimed in claim 1, wherein: in the step (3), the adding amount of the magnesium oxide is controlled at 15 percent.
7. The method of preparing a modified magnesium sulfate cement as claimed in claim 4, wherein: the additive is preferably citric acid or sodium citrate.
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| CN110357467A (en) * | 2019-07-15 | 2019-10-22 | 辽宁科大中驰镁建材科技有限公司 | A kind of modification magnesium sulfate cement and preparation method thereof that resistant to sea water corrodes |
| CN110218011A (en) * | 2019-07-26 | 2019-09-10 | 南乐县美誉达建材有限公司 | A kind of technique of industrial waste sulfuric acid production plate |
| CN113698171B (en) * | 2021-09-08 | 2022-06-14 | 山西大学 | Surface-hydrophobic modified magnesium-based fly ash porous sound absorption material and preparation method thereof |
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