CN111333362A - Low-dosage high-early-strength alkali-free liquid accelerator and preparation method thereof - Google Patents
Low-dosage high-early-strength alkali-free liquid accelerator and preparation method thereof Download PDFInfo
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- CN111333362A CN111333362A CN202010163119.6A CN202010163119A CN111333362A CN 111333362 A CN111333362 A CN 111333362A CN 202010163119 A CN202010163119 A CN 202010163119A CN 111333362 A CN111333362 A CN 111333362A
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
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Abstract
The alkali-free liquid accelerator is prepared from the following raw materials: 50-60% of modified aluminum sulfate, 2-4% of fluorine aluminum complex solution, 3-6% of organic cosolvent, 1-2% of pH regulator, 0.5-1.5% of inorganic stabilizer, 0.3-0.5% of viscosity regulator, 4-6% of composite early strength agent and the balance of water, wherein the sum of the mass percentages of the components is 100%. The invention also provides a preparation method of the alkali-free liquid accelerator. The alkali-free liquid accelerator is simple in preparation process, free of hydrofluoric acid, alkali, chlorine and corrosion of steel bars, free of environmental pollution and harm to bodies of operators, can meet the technical requirements of GB/T35159-2017 on the alkali-free accelerator when the mixing amount of the alkali-free liquid accelerator is 5% -6%, has the compression strength of more than or equal to 13.0MPa in 1 day, and has the characteristics of low mixing amount, good stability, high early strength and high later strength retention rate.
Description
Technical Field
The invention relates to a concrete admixture, in particular to a low-dosage high-early-strength alkali-free liquid accelerator. The invention also relates to a preparation method of the low-dosage high-early-strength alkali-free liquid accelerator.
Background
In recent years, the sprayed concrete plays more and more important roles in infrastructure construction and urban construction engineering in China, and the consumption of the sprayed concrete is in an increasing trend. Particularly, with the increasing construction of tunnels in the process of constructing high-speed railways and highways in western regions of China, higher and higher requirements on the performance, durability and the like of sprayed concrete are provided. The accelerator is an indispensable additive for sprayed concrete, and has the functions of accelerating the setting and hardening of the sprayed concrete, reducing the rebound loss, preventing the sprayed concrete from falling off due to gravity and improving the early strength of the concrete. The development of accelerators has undergone the development history of powdery overbased, powdery low-alkaline, liquid overbased, liquid low-alkaline and liquid alkali-free accelerators. The alkali-free liquid accelerator has low alkali content and low corrosivity, does not influence the later strength and durability of concrete, and is a future development direction of accelerator products.
However, most of the current alkali-free liquid accelerator products adopt industrial-grade aluminum sulfate as a main accelerating component, and the following problems are generally existed: (1) the mixing amount is higher. Because the solubility of the aluminum sulfate is low, the solid content of the quick-setting agent is not high, the doping amount is high, and the use cost is high; (2) the stability is poor. The aluminum ions are easy to hydrolyze in water, so that the stability of the accelerator is poor, and long-distance transportation and long-time storage are not facilitated; (3) the early strength is low. The alkali-free accelerator has various components, wherein the early strength is easily low due to the use of some fluorides, stabilizers and acids, the compressive strength of the mortar is less than 7.0MPa in 1 day, and the alkali-free accelerator does not meet the requirements of GB/T35159-2017 standards. Therefore, the liquid accelerator with low mixing amount, high early strength, high later strength guarantee rate and good stability becomes a necessary trend for the development of alkali-free liquid accelerators in the future.
The inventors searched the following related patent documents: CN107601943A discloses an alkali-free liquid accelerator and a preparation method thereof, wherein the alkali-free liquid accelerator is prepared from the following raw materials: aluminum sulfate, ferrous sulfate, sodium fluoride, magnesium fluosilicate, precipitated hydrated magnesium silicate, diethanol amine and water. The accelerator has good accelerating effect, can effectively shorten the accelerating and final setting time of concrete, and effectively improves the early strength and the later strength of the concrete. The preparation method of the alkali-free liquid accelerator comprises the steps of stirring water and precipitated hydrated magnesium silicate at 40 ℃ for 15-20 min, adding ferrous sulfate and sodium fluoride, mixing and stirring for 8-15 min, adding aluminum sulfate, heating to 75-85 ℃, reacting for 1h, adding magnesium fluosilicate, stirring for 20-40 min, adding diethanolamine, and stirring for 18-25 min to obtain the alkali-free liquid accelerator. CN110078403A discloses an ultra-early-strength alkali-free liquid accelerator and a preparation method thereof, wherein the accelerator comprises the following raw materials, by mass, 32-42% of aluminum sulfate, 10-20% of hydrated calcium silicate, 3-5% of lithium fluosilicate, 4-8% of triisopropanolamine, 1-3% of a pH regulator, 1-2% of a suspending agent, and the balance of water, and the total amount is 100%. The ultra-early-strength alkali-free liquid accelerator can be used in a sprayed concrete wet spraying process. The stabilization period exceeds five months, the setting time is met under the mixing amount of 5-7%, the 6h strength of different types of cement can reach 2.8MPa, the 12h strength reaches 6MPa, the 1d strength exceeds 20MPa, the 28-day compressive strength ratio reaches 108%, and the 90-day compressive strength retention rate reaches 115%. CN110255955A discloses an alkali-free liquid accelerator and a preparation method and application thereof, wherein the alkali-free liquid accelerator comprises the following components in percentage by mass: aluminum sulfate: 45% -55%, nano alumina: 5% -10%, hydrofluoric acid: 5% -10%, solubilizing component: 3% -7%, fluorosilicate: 2% -6%, early strength component: 1% -4%, stabilizing components: 0.5-1%, water: 20 to 32 percent. The alkali-free liquid accelerator disclosed by the invention takes aluminum sulfate as a main raw material, and is matched with nano aluminum oxide, hydrofluoric acid, a solubilizing component, fluorosilicate, an early strength component and a stabilizing component, so that the alkali-free liquid accelerator has a good accelerating effect, long-term stability and lower rebound rate, and under the doping amount of 7%, all performances of the alkali-free liquid accelerator meet the requirements of a standard JC477-2005 accelerator for sprayed concrete on an first-class accelerator.
The technologies have the advantages that the preparation process of the alkali-free liquid accelerator is simple, hydrofluoric acid is not contained, alkali is not contained, chlorine is not contained, steel bars are not corroded, the environment is not polluted, the body of an operator is not damaged, and meanwhile, the alkali-free liquid accelerator is low in doping amount and good in stability, and a specific guidance scheme is not given.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-dosage high-early-strength alkali-free liquid accelerator which has good performance, simple preparation process, no hydrofluoric acid, no alkali, no chlorine, no corrosion to steel bars, no environmental pollution and no harm to the body of operators, can meet the technical requirements of GB/T35159-2017 on the alkali-free accelerator when the dosage of the alkali-free liquid accelerator is 5-6 percent, has the compressive strength of more than or equal to 13.0MPa in 1 day, and has the characteristics of low dosage, good stability, high early strength and high later strength retention rate.
Therefore, the invention also provides a preparation method of the low-dosage high-early-strength alkali-free liquid accelerator.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the alkali-free liquid accelerator with low mixing amount and high early strength is prepared from the following raw materials in percentage by mass: 50-60% of modified aluminum sulfate, 2-4% of fluorine-aluminum complex solution, 3-6% of organic cosolvent, 1-2% of pH regulator, 0.5-1.5% of inorganic stabilizer, 0.3-0.5% of viscosity regulator, 4-6% of composite early strength agent and the balance of water, wherein the sum of the mass percentages of the components is 100%. The modified aluminum sulfate is prepared by mixing and grinding industrial aluminum sulfate with the aluminum oxide content of more than or equal to 16.0% and pseudo-boehmite, and the mass ratio of the industrial aluminum sulfate to the pseudo-boehmite is as follows: industrial aluminum sulfate, namely pseudo boehmite (10-9): 1; the fluorine-aluminum complex solution is prepared by stirring water, fluosilicic acid and industrial aluminum hydroxide according to the mass ratio of (1.5-1.8) to (2.5-2.8) to 1 at normal temperature for 20-30 min; the organic cosolvent is formed by mixing one or two of diethanolamine and triethanolamine with glycerol according to the mass ratio of (1.8-2) to 1, and the mixing ratio is arbitrary when the diethanolamine and the triethanolamine are combined; feeding the organic cosolvent in a constant-speed dropwise adding mode in the preparation process of the alkali-free accelerator; the inorganic stabilizer is one or more of hydrated magnesium silicate (ultrafine powder), sepiolite and magnesium aluminum silicate; the composite early strength agent is formed by compounding lithium nitrate and calcium silicate hydrate nano suspension, wherein the lithium nitrate accounts for 1-5% of the total mass of the composite early strength agent, and the calcium silicate hydrate nano suspension is milky dispersion liquid which is artificially synthesized by an in-situ precipitation method and has the solid content of 15-20% and the size of 100-250 nm of nano calcium silicate.
The preparation method of the low-doping high-early-strength alkali-free liquid accelerator comprises the following process steps of ① mixing and grinding industrial aluminum sulfate and pseudo-boehmite according to a mass ratio of (10-9): 1, sieving the mixture with a sieve of 80-100 meshes to obtain modified aluminum sulfate, ② preparing a fluorine-aluminum complex solution, namely, adding water, fluosilicic acid and industrial aluminum hydroxide into a reaction container according to a mass ratio of (1.5-1.8) to (2.5-2.8) to 1 in sequence, stirring the mixture at normal temperature for 20-30 min to obtain a fluorine-aluminum complex solution, ③ adding water into the reaction container, then adding the modified aluminum sulfate prepared in the step ①, stirring the mixture at normal temperature, slowly dropwise adding an organic cosolvent (the dropwise adding time is 45-60 min), continuously stirring the mixture for 1.5-2 h (continuously stirring the mixture for 1.5-2 h from the dropwise adding), preparing a solution A, ④ slowly adding the fluorine-aluminum complex solution prepared in the step ② into the solution A prepared in the step ③, stirring the solution at normal temperature for 20-30 min, then adding a viscosity regulator, and stirring the early-strength liquid accelerator for 20min, and finally adding the alkali-10 high-early-strength accelerator.
In the above technical solution, a preferable technical solution may be: the pH regulator is one or a combination of more of citric acid, phosphoric acid and formic acid, and the mixture ratio is arbitrary when the pH regulator is combined. The viscosity regulator is one or the combination of two of hydroxyethyl cellulose and welan gum, and the proportion of the viscosity regulator is arbitrary when the viscosity regulator is combined. In the preparation process of the low-doping high-early-strength alkali-free liquid accelerator, the stirring temperature is normal temperature, and the stirring rotating speed is 1000-1200 rpm.
In the above technical solutions, preferred technical solutions can also be seen in examples 1 to 4.
The mixing amount of the low-mixing-amount high-early-strength alkali-free liquid accelerator in the sprayed concrete is 5-6% of the total mass of the cementitious material.
The alkali-free liquid accelerator preferably selects each functional component and carries out appropriate modification, adopts the normal-temperature synthesis and mechanical stirring process, improves the aluminum content in the accelerator by modifying aluminum sulfate and introducing an organic cosolvent, and accelerates the hydration of cement and shortens the setting time of the cement by introducing a large amount of aluminum ions into the modified aluminum sulfate and fluorine-aluminum complex double components simultaneously as main coagulation accelerating components. The fluorine ions introduced by the fluorine-aluminum complex compound have a certain coagulation accelerating effect, so that the accelerator can meet the standard requirement at a lower dosage. By adding the pH regulator and the inorganic stabilizer, the pH regulator effectively inhibits hydrolysis-precipitation of aluminum ions and ensures the concentration of the aluminum ions in the solution; the inorganic stabilizer has a microfiber needle structure, so that the inorganic stabilizer can be well dispersed in a system to form a three-dimensional network structure, the uniformity of the accelerator is improved, and the stability of the accelerator is greatly improved under the combined action of the two aspects. The composite early strength agent effectively makes up the problem of low early strength caused by a pH regulator and fluorine ions, but can greatly improve the early strength without reducing the retention rate of later strength.
Compared with the prior art, the alkali-free liquid accelerator has the following advantages: (1) the mixing amount is low. The doping amount of the alkali-free liquid accelerator is generally 6-9% of the total amount of the cementing material, and the special modified aluminum sulfate and the fluorine aluminum complex are used as main accelerating components, so that the effective aluminum ion content in the accelerator is greatly improved, and the cement setting time of the accelerator can meet the requirement of GB/T35159-2017 standard under the condition of lower doping amount of 5-6%. (2) High early strength and high retention rate of later strength. According to the invention, by optimizing the early-strength components suitable for the accelerating agent and innovatively adopting the lithium nitrate and the calcium silicate hydrate nano suspension to form the composite early-strength agent, the early strength is improved, the compressive strength of the mortar can reach more than 13MPa in 1 day, and the retention rate of the later strength is high. (3) The stability is good. The invention preferably selects the inorganic stabilizer and the pH regulator, improves the stability of the accelerator from the physical and chemical aspects, and has a stabilization period (shelf life) of more than 180 days. (4) Low cost and simple preparation process. The invention adopts the cheaper fluosilicic acid raw material to replace the commonly used hydrofluoric acid with stronger toxicity and corrosivity, has simple preparation process, does not need heating, further saves the cost, and has reduced the production cost by more than 15 percent through tests.
In conclusion, the alkali-free liquid accelerator disclosed by the invention is good in performance, simple in preparation process, free of hydrofluoric acid, alkali, chlorine and corrosion on steel bars, free of environmental pollution and free of harm to bodies of operators, and meanwhile, the alkali-free liquid accelerator can meet the technical requirements of GB/T35159-2017 on the alkali-free accelerator when the mixing amount of the alkali-free liquid accelerator is 5% -6%, the compressive strength of 1 day is more than or equal to 13.0MPa, and the alkali-free liquid accelerator has the characteristics of low mixing amount, good stability, high early strength and high retention rate of later strength.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The low-doped high-early-strength alkali-free liquid accelerator is prepared by adding 50% of modified aluminum sulfate, 4% of a fluorine aluminum complex solution, 3% of an organic cosolvent, 1% of a pH regulator, 0.5% of an inorganic stabilizer, 0.5% of a viscosity regulator, 6% of a composite early-strength agent and 35% of water by mass percentage, wherein the sum of the mass percentages of the modified aluminum sulfate and the composite early-strength agent is 100%, the modified aluminum sulfate is prepared by mixing and grinding industrial aluminum sulfate and pseudo-thin aluminum hydroxide with aluminum trioxide content being more than or equal to 16.0%, the mass ratio of the modified aluminum sulfate to the pseudo-thin aluminum hydroxide is that the industrial aluminum sulfate is that the pseudo-thin aluminum hydroxide is that the industrial aluminum sulfate is not less than 16.0%, the fluorine aluminum sulfate is that the industrial aluminum sulfate is that the fluosilicic acid is that the industrial aluminum hydroxide is prepared according to the mass ratio of 1.5: 2: 1.5: 1, the organic cosolvent is prepared by mixing and the ammonium sulfate and the calcium silicate is that is prepared by adding the ammonium sulfate and ammonium silicate, the ammonium silicate is that is prepared by mixing and ammonium silicate, the ammonium silicate is prepared by adding the ammonium silicate, the ammonium silicate is that is prepared by mixing and ammonium silicate, the ammonium silicate is that is prepared by adding the ammonium silicate, the ammonium silicate is prepared by mixing and the ammonium silicate, the.
The low-doped high-early-strength alkali-free liquid accelerator is prepared by adding 55 mass percent of modified aluminum sulfate, 3 mass percent of a fluorine-aluminum complex solution, 4 mass percent of an organic cosolvent, 1.5 mass percent of a pH regulator, 1.0 mass percent of an inorganic stabilizer, 0.5 mass percent of a viscosity regulator, 5 mass percent of a composite early-strength agent and 30 mass percent of water into a low-early-strength alkali-free liquid accelerator, wherein the modified aluminum sulfate is prepared by mixing and grinding industrial aluminum sulfate with aluminum trioxide content being more than or equal to 16.0% and pseudo-boehmite according to the mass percent of 100%, the mass ratio of the industrial aluminum sulfate to the pseudo-boehmite is that the industrial aluminum sulfate is mixed and ground into a low-early-strength alkali-free liquid accelerator, the modified aluminum sulfate is prepared by adding 50 mass percent of the low-early-strength alkali-free liquid accelerator, the low-early-strength alkali-free liquid accelerator is prepared by adding 50 mass percent of the low-early-strength alkali-free liquid accelerator, the low-early-strength alkali-early-strength liquid accelerator is prepared by mixing the steps of a low-early-strength liquid accelerator, the low-early-strength liquid accelerator is prepared by adding ammonium sulfate and stirring slow-early.
Example 3: the low-dosage high-early-strength alkali-free liquid accelerator is prepared from the following raw materials in percentage by mass: 60% of modified aluminum sulfate, 3% of fluorine-aluminum complex solution, 6% of organic cosolvent, 2% of pH regulator, 0.7% of inorganic stabilizer, 0.3% of viscosity regulator, 5% of composite early strength agent and 23% of water, wherein the sum of the mass percentages of the components is 100%. The modified aluminum sulfate is prepared by mixing and grinding industrial aluminum sulfate with the aluminum oxide content of more than or equal to 16.0% and pseudo-boehmite, and the mass ratio of the industrial aluminum sulfate to the pseudo-boehmite is as follows: industrial aluminum sulfate, pseudo-boehmite 9: 1; the fluorine-aluminum complex solution is prepared by stirring water, fluosilicic acid and industrial aluminum hydroxide for 30min at normal temperature according to the mass ratio of 1.5:2.5: 1; the organic cosolvent is formed by mixing diethanolamine and glycerol according to the mass ratio of 2: 1; the pH regulator is citric acid; the inorganic stabilizer is hydrated magnesium silicate; the viscosity regulator is hydroxyethyl cellulose; the composite early strength agent is prepared by mixing lithium nitrate and calcium silicate hydrate nano suspension, wherein the lithium nitrate accounts for 2% of the total mass of the composite early strength agent, the calcium silicate hydrate nano suspension is milky dispersion liquid which is artificially synthesized by an in-situ precipitation method and has the solid content of 18% -19% and the size of nano calcium silicate of 100-150 nm, and the calcium silicate hydrate nano suspension accounts for 95% of the total mass of the composite early strength agent. The preparation method of the low-dosage high-early-strength alkali-free liquid accelerator is the same as that of the example 1.
Example 4: the low-dosage high-early-strength alkali-free liquid accelerator is prepared from the following raw materials in percentage by mass: 57% of modified aluminum sulfate, 2% of fluorine-aluminum complex solution, 5% of organic cosolvent, 1.5% of pH regulator, 1.2% of inorganic stabilizer, 0.3% of viscosity regulator, 4% of composite early strength agent and 29% of water, wherein the sum of the mass percentages of the components is 100%. The modified aluminum sulfate is prepared by mixing and grinding industrial aluminum sulfate with the aluminum oxide content of more than or equal to 16.0% and pseudo-boehmite, and the mass ratio of the industrial aluminum sulfate to the pseudo-boehmite is as follows: industrial aluminum sulfate, pseudo-boehmite 9: 1; the fluorine-aluminum complex solution is prepared by stirring water, fluosilicic acid and industrial aluminum hydroxide for 20min at normal temperature according to the mass ratio of 1.5:2.5: 1; the organic cosolvent is formed by mixing triethanolamine and glycerol according to the mass ratio of 2: 1; the pH regulator is formic acid; the inorganic stabilizer is aluminum magnesium silicate; the viscosity regulator is a rubber cement; the composite early strength agent is prepared by mixing lithium nitrate and calcium silicate hydrate nano suspension, wherein the lithium nitrate accounts for 4% of the total mass of the composite early strength agent, the calcium silicate hydrate nano suspension is milky dispersion liquid which is artificially synthesized by an in-situ precipitation method and has the solid content of 18% -19% and the size of nano calcium silicate of 100-150 nm, and the calcium silicate hydrate nano suspension accounts for 96% of the total mass of the composite early strength agent. The preparation method of the low-dosage high-early-strength alkali-free liquid accelerator is the same as that of the embodiment 2.
The following is the experimental part of the invention (application examples):
the mixing amount of the accelerator in the sprayed concrete is 5-6% of the total amount of the cementing material. According to the detection method specified in GB/T35159-. The performance index requirements of GB/T35159-2017 on the alkali-free accelerator are shown in Table 1. The test results of the above examples are shown in table 2. The cement used in the test is the standard cement, and the sand is the standard sand.
Table 1 GB/T35159-2017 performance requirements for alkali-free setting accelerators
TABLE 2 detection results of the accelerators
As can be seen from the data in Table 2, the alkali-free liquid accelerator disclosed by the invention has the doping amount of 5-6% (lower than 6-9% of the standard requirement), each performance index meets the performance requirement of GB/T35159-2017 in Table 1 on the alkali-free accelerator, and the compressive strength is far greater than 7.0MPa in 1 day. The comparative example has the advantage that the setting time is faster under the same dosage, but the 1-day compressive strength is too low to meet the standard requirement.
In conclusion, the alkali-free liquid accelerator disclosed by the invention has the advantages of good performance, simple preparation process, no hydrofluoric acid, no alkali, no chlorine, no corrosion to steel bars, no environmental pollution and no harm to bodies of operators, can meet the technical requirements of GB/T35159-2017 on the alkali-free liquid accelerator when the doping amount is 5% -6%, has the compressive strength of more than or equal to 13.0MPa in 1 day, has the characteristics of low doping amount, good stability, high early strength and high later strength retention rate, and belongs to a low-doping amount high-early strength alkali-free liquid accelerator.
Claims (10)
1. The low-dosage high-early-strength alkali-free liquid accelerator is characterized by being prepared from the following raw materials in percentage by mass: 50-60% of modified aluminum sulfate, 2-4% of fluorine aluminum complex solution, 3-6% of organic cosolvent, 1-2% of pH regulator, 0.5-1.5% of inorganic stabilizer, 0.3-0.5% of viscosity regulator, 4-6% of composite early strength agent and the balance of water, wherein the sum of the mass percentages of the components is 100%;
the modified aluminum sulfate is prepared by mixing and grinding industrial aluminum sulfate with the aluminum oxide content of more than or equal to 16.0% and pseudo-boehmite, and the mass ratio of the industrial aluminum sulfate to the pseudo-boehmite is as follows: industrial aluminum sulfate, namely pseudo-boehmite (10-9): 1; the fluorine-aluminum complex solution is prepared by stirring water, fluosilicic acid and industrial aluminum hydroxide according to the mass ratio of (1.5-1.8) to (2.5-2.8) to 1 at normal temperature for 20-30 min; the organic cosolvent is formed by mixing one or two of diethanolamine and triethanolamine with glycerol according to the mass ratio of (1.8-2): 1, and the mixing ratio of the diethanolamine and the triethanolamine is arbitrary when combined; the inorganic stabilizer is one or a combination of more of hydrated magnesium silicate, sepiolite and magnesium aluminum silicate; the composite early strength agent is formed by compounding lithium nitrate and calcium silicate hydrate nano suspension, wherein the lithium nitrate accounts for 1-5% of the total mass of the composite early strength agent, and the calcium silicate hydrate nano suspension is milky dispersion liquid which is artificially synthesized by an in-situ precipitation method and has the solid content of 15-20% and the size of nano calcium silicate of 100-250 nm;
① mixing and grinding industrial aluminum sulfate and pseudo-boehmite according to the mass ratio of (10-9): 1, sieving the mixture with a sieve of 80-100 meshes to prepare modified aluminum sulfate, ② preparing a fluorine-aluminum complex solution, namely, adding water, fluosilicic acid and industrial aluminum hydroxide according to the mass ratio of (1.5-1.8): 2.5-2.8): 1 in sequence, stirring the mixture at normal temperature for 20-30 min to prepare a fluorine-aluminum complex solution, ③ adding water into a reaction vessel, then adding the modified aluminum sulfate prepared in the step ①, stirring the mixture at normal temperature while slowly dropwise adding an organic cosolvent, continuously stirring the mixture for 1.5-2 h to prepare a solution A, ④ slowly adding the fluorine-aluminum complex solution prepared in the step ② into the solution A prepared in the step ③, stirring the mixture at normal temperature for 20-30 min, then sequentially adding a pH regulator, an inorganic stabilizer and a viscosity regulator into the solution A prepared in the step ③, stirring the mixture at normal temperature for 20-30 min, and finally adding a early strength admixture, namely, stirring the low-alkali-free liquid.
2. The alkali-free liquid accelerator with low dosage and high early strength as claimed in claim 1, wherein the pH regulator is one or more of citric acid, phosphoric acid and formic acid, and the ratio of the pH regulator to the citric acid, the phosphoric acid and the formic acid is arbitrary.
3. The alkali-free liquid accelerator with low dosage and high early strength as claimed in claim 1, wherein the viscosity modifier is one or a combination of two of hydroxyethyl cellulose and welan gum, and the ratio of the combination is arbitrary.
4. The low-dosage high-early-strength alkali-free liquid accelerator as claimed in claim 1, wherein the stirring temperature and the stirring speed are both normal temperature and 1000-1200 rpm in the preparation process of the low-dosage high-early-strength alkali-free liquid accelerator.
5. The low-doped high-early-strength alkali-free liquid accelerator as claimed in claim 1 is prepared by adding 50% of modified aluminum sulfate, 4% of a fluorine aluminum complex solution, 3% of an organic cosolvent, 1% of a pH regulator, 0.5% of an inorganic stabilizer, 0.5% of a viscosity regulator, 6% of a composite early strength agent and 35% of water by mass percentage, wherein the sum of the mass percentages of the modified aluminum sulfate and the viscosity regulator is 100%, the modified aluminum sulfate is prepared by mixing and grinding industrial aluminum sulfate with aluminum oxide content being more than or equal to 16.0% and pseudo-boehmite according to a mass ratio of water to fluosilicic acid to the pseudo-boehmite 1: 2.5:1, the organic aluminum complex solution is prepared by mixing diethanolamine and glycerol according to a mass ratio of 2:1, the pH regulator is phosphoric acid, the inorganic stabilizer is sepiolite, the viscosity regulator is prepared by hydroxyethyl cellulose, the composite early strength agent is prepared by adding 395 to the industrial aluminum hydroxide, the composite early strength agent is prepared by mixing and stirring a slow-stirring process of a slow-stirring ammonium sulfate, the low-early-strength liquid accelerator is prepared by adding 50.5% of a slow-early-strength aluminum sulfate, the low-early-strength liquid accelerator is prepared by stirring a slow-early-strength liquid accelerator by stirring process of a slow-early.
6. The low-doped high-early-strength alkali-free liquid accelerator is prepared by the following steps of adding 55 mass percent of modified aluminum sulfate, 3 mass percent of a fluorine-aluminum complex solution, 4 mass percent of an organic cosolvent, 1.5 mass percent of a pH regulator, 1.0 mass percent of an inorganic stabilizer, 0.5 mass percent of a viscosity regulator, 5 mass percent of a composite early-strength agent and 30 mass percent of water into a low-early-strength alkali-free liquid accelerator according to claim 1, stirring the low-doped high-early-strength alkali-free liquid accelerator in a normal-temperature mixing process, adding 150 mass percent of a low-early-strength alkali-free liquid accelerator, stirring the low-early-strength alkali-free liquid accelerator and a normal-temperature mixing process, stirring the low-early-strength alkali-free liquid accelerator and the normal-temperature mixing process, wherein the low-early-strength alkali-free liquid accelerator is prepared by adding 50 mass percent of a low-early-strength alkali-free liquid accelerator, the low-early-strength-free liquid accelerator and the inorganic stabilizer, the low-early-strength alkali-early-strength liquid accelerator is prepared by adding a low-early-strength liquid accelerator, stirring the low-early-strength agent, stirring early-strength liquid accelerator is prepared by adding calcium silicate liquid accelerator according to a 5 inorganic calcium silicate liquid accelerator, stirring process, wherein the low-early-calcium silicate slow calcium silicate stabilizing accelerator is prepared by adding ammonium silicate slow calcium silicate synthesis accelerator is prepared by adding ammonium silicate synthesis accelerator, the low-calcium silicate slow calcium silicate.
7. The low-dosage high-early-strength alkali-free liquid accelerator as claimed in claim 1, which is prepared from the following raw materials in percentage by mass: 60% of modified aluminum sulfate, 3% of fluorine-aluminum complex solution, 6% of organic cosolvent, 2% of pH regulator, 0.7% of inorganic stabilizer, 0.3% of viscosity regulator, 5% of composite early strength agent and 23% of water, wherein the sum of the mass percentages of the components is 100%; the modified aluminum sulfate is prepared by mixing and grinding industrial aluminum sulfate with the aluminum oxide content of more than or equal to 16.0% and pseudo-boehmite, and the mass ratio of the industrial aluminum sulfate to the pseudo-boehmite is as follows: industrial aluminum sulfate, pseudo-boehmite 9: 1; the fluorine-aluminum complex solution is prepared by stirring water, fluosilicic acid and industrial aluminum hydroxide for 30min at normal temperature according to the mass ratio of 1.5:2.5: 1; the organic cosolvent is formed by mixing diethanolamine and glycerol according to the mass ratio of 2: 1; the pH regulator is citric acid; the inorganic stabilizer is hydrated magnesium silicate; the viscosity regulator is hydroxyethyl cellulose; the composite early strength agent is prepared by mixing lithium nitrate and calcium silicate hydrate nano suspension, wherein the lithium nitrate accounts for 2% of the total mass of the composite early strength agent, and the calcium silicate hydrate nano suspension is milky dispersion which is artificially synthesized by an in-situ precipitation method and has the solid content of 18% -19% and the size of 100-150 nm of nano calcium silicate.
8. The low-dosage high-early-strength alkali-free liquid accelerator as claimed in claim 1, which is prepared from the following raw materials in percentage by mass: 57% of modified aluminum sulfate, 2% of fluorine-aluminum complex solution, 5% of organic cosolvent, 1.5% of pH regulator, 1.2% of inorganic stabilizer, 0.3% of viscosity regulator, 4% of composite early strength agent and 29% of water, wherein the sum of the mass percentages of the components is 100%; the modified aluminum sulfate is prepared by mixing and grinding industrial aluminum sulfate with the aluminum oxide content of more than or equal to 16.0% and pseudo-boehmite, and the mass ratio of the industrial aluminum sulfate to the pseudo-boehmite is as follows: industrial aluminum sulfate, pseudo-boehmite 9: 1; the fluorine-aluminum complex solution is prepared by stirring water, fluosilicic acid and industrial aluminum hydroxide for 20min at normal temperature according to the mass ratio of 1.5:2.5: 1; the organic cosolvent is formed by mixing triethanolamine and glycerol according to the mass ratio of 2: 1; the pH regulator is formic acid; the inorganic stabilizer is aluminum magnesium silicate; the viscosity regulator is a rubber cement; the composite early strength agent is prepared by mixing lithium nitrate and calcium silicate hydrate nano suspension, wherein the lithium nitrate accounts for 4% of the total mass of the composite early strength agent, and the calcium silicate hydrate nano suspension is milky dispersion which is artificially synthesized by an in-situ precipitation method and has the solid content of 18% -19% and the size of 100-150 nm of nano calcium silicate.
9. A preparation method of a low-dosage high-early-strength alkali-free liquid accelerator as claimed in claim 1 is characterized by comprising the following process steps of ① mixing and grinding industrial aluminum sulfate and pseudo-boehmite according to a mass ratio of (10-9): 1, and sieving the mixture with a sieve of 80-100 meshes to obtain modified aluminum sulfate, ② preparing a fluorine-aluminum complex solution, namely adding water, fluosilicic acid and industrial aluminum hydroxide in sequence according to a mass ratio of (1.5-1.8): 2.5-2.8): 1, stirring the mixture at normal temperature for 20-30 min to obtain a fluorine-aluminum complex solution, ③ adding water into a reaction vessel, then adding the modified aluminum sulfate prepared in the step ①, stirring the mixture at normal temperature, slowly dropwise adding an organic cosolvent, continuously stirring for 1.5-2 h to obtain a solution A, ④ slowly adding the fluorine-aluminum complex solution prepared in the step ② into the solution A prepared in the step ③, stirring the solution for 20-30 min, then sequentially adding a pH regulator, a viscosity regulator, stirring the early-strength accelerator, and the early-strength admixture liquid accelerator, and finally adding the low-early-alkali-free liquid accelerator, namely the low-early-alkali-free liquid accelerator, stirring liquid accelerator.
10. The method for preparing the alkali-free liquid accelerator with low dosage and high early strength as claimed in claim 9, wherein the pH regulator is one or more of citric acid, phosphoric acid and formic acid, and the mixture ratio is arbitrary when the pH regulator is combined with the citric acid, the phosphoric acid and the formic acid; the viscosity regulator is one or the combination of two of hydroxyethyl cellulose and a rubber for a warm wheel, and the mixture ratio is arbitrary when the viscosity regulator is combined; in the preparation process of the low-doping high-early-strength alkali-free liquid accelerator, the stirring temperature is normal temperature, and the stirring rotating speed is 1000-1200 rpm.
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