CN114057422A - Alkali-free fluorine-free chlorine-free liquid concrete accelerator and preparation method thereof - Google Patents
Alkali-free fluorine-free chlorine-free liquid concrete accelerator and preparation method thereof Download PDFInfo
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- CN114057422A CN114057422A CN202111577792.5A CN202111577792A CN114057422A CN 114057422 A CN114057422 A CN 114057422A CN 202111577792 A CN202111577792 A CN 202111577792A CN 114057422 A CN114057422 A CN 114057422A
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses an alkali-free fluorine-free chlorine-free liquid concrete accelerator and a preparation method thereof, and relates to the technical field of environment-friendly concrete accelerators. The raw materials comprise 45-55% of aluminum sulfate, 1.5-2.5% of modified regulator, 3.5-5% of diethanolamine, 2-2.5% of magnesium sulfate, 1-3% of calcium formate and 1-2% of urea. The balance of water. Weighing the raw materials in proportion, adding water into a reaction kettle, heating while stirring, and gradually adding aluminum sulfate; after the temperature is controlled to be 55-65 ℃, sequentially adding magnesium sulfate and calcium formate every 5-8 min, and continuously stirring for reacting for 1.5-2 h; and naturally cooling to normal temperature, adding urea, a modification regulator and diethanolamine, stirring for 20-30 min, and controlling the pH of the accelerator solution to be 2.5-3 to obtain the finished product of the liquid concrete accelerator. The final product is transparent uniform liquid with density of 1.15g/cm3～1.2g/cm3Can greatly reduce the risk of concrete alkali-aggregate reactionAll raw materials do not contain chloride ions, fluoride ions and sodium ions, so that the corrosion of the raw materials on reinforced concrete is reduced.
Description
Technical Field
The invention relates to the technical field of environment-friendly concrete accelerators, in particular to an alkali-free fluorine-free chlorine-free liquid concrete accelerator and a preparation method thereof.
Background
The concrete accelerator is an additive which can quickly set and harden concrete when being doped into the concrete, and is used for being mixed in sprayed concrete in projects such as mine well projects, railway tunnels, diversion culverts, underground engineering and the like. The traditional accelerator mainly contains alkali, chlorine, fluorine and powder, has strong corrosivity, particularly causes the problems of concrete alkali aggregate reaction, steel bar corrosion and the like due to the existence of free states of fluorine, chlorine and the like, has high requirements on construction equipment, seriously influences the later strength and the anti-carbonization durability of concrete, and damages the human health of production and constructors. In recent years, the development of alkali-free and chlorine-free accelerator has been advanced, but most of accelerator products still contain free fluorine, which affects the performance of concrete and is harmful to human health, as mentioned above.
Disclosure of Invention
The invention aims to provide an alkali-free fluorine-free chlorine-free liquid concrete accelerator and a preparation method thereof, and solves the problem that alkali chlorine and fluorine in the conventional accelerator have adverse effects on the performance of concrete and human health.
In order to solve the technical problems, the invention adopts the following technical scheme: an alkali-free fluoride-free chlorine-free liquid concrete accelerator is characterized in that: the raw materials consist of aluminum sulfate, a modified regulator, magnesium sulfate, calcium formate, urea and water; the raw materials comprise the following components in percentage by mass:
the balance of water;
wherein the modifying and regulating agent is prepared by stirring and reacting diethanol amine, triethanolamine, tartaric acid, glycerol, ethyl acetate and concentrated sulfuric acid.
The further technical scheme is that the quantity ratio of diethanolamine, triethanolamine, tartaric acid, glycerol, ethyl acetate and concentrated sulfuric acid in the modifying and regulating agent is 2:1:1:1:0.5: 0.05.
The further technical scheme is that the raw materials comprise the following components in percentage by mass:
the balance of water.
The further technical scheme is that the preparation method of the concrete accelerator comprises the following steps: weighing the raw materials in proportion, adding water into a reaction kettle, heating while stirring, and gradually adding aluminum sulfate; after the temperature is controlled to be 55-65 ℃, sequentially adding magnesium sulfate and calcium formate every 5-8 min, and continuously stirring for reacting for 1.5-2 h; and naturally cooling to normal temperature, adding urea, a modification regulator and diethanolamine, stirring for 20-30 min, and controlling the pH of the accelerator solution to be 2.5-3 to obtain the finished product of the liquid concrete accelerator.
The further technical proposal is that the preparation method of the modified regulator comprises the following steps: weighing the raw materials according to the proportion, feeding the raw materials while stirring according to the sequence of diethanolamine, triethanolamine, tartaric acid, glycerol, ethyl acetate and concentrated sulfuric acid, wherein the interval time of each feeding is 5-10 min, stirring the raw materials for 25-35 min after all the raw materials are added, and controlling the whole reaction process at 65-70 ℃ to prepare the mixed long-chain type modifying regulator.
The further technical proposal is that the stirring speed is 300r/min to 500 r/min.
Compared with the prior art, the invention has the beneficial effects that:
the regulator is prepared by taking diethanolamine, triethanolamine, tartaric acid, glycerol, ethyl acetate and concentrated sulfuric acid as catalysts, the polyhydroxyhydramine ester regulator generated by the reaction can be mutually soluble with water, forms stable soluble complex ions with metal ions, and forms a soluble zone by complexing with the metal ions in cement, thereby greatly improving the diffusion rate of hydration products and promoting the hydration of cement. The ester group in the concrete accelerator increases the mobile phase, slump retaining property, low shrinkage and environmental protection property of the concrete accelerator, thereby increasing the frost resistance and stability of the accelerator, shortening the initial and final setting time of concrete to a certain extent, and increasing the strength of the concrete
The liquid concrete accelerator obtained by the invention has good quick setting effect, the initial setting time is 1.5-4 min, the final setting time is 6-10 min, the early strength development is fast, the 28-day strength ratio reaches or even exceeds 100%, in addition, the liquid alkali-free fluorine-free chlorine-free accelerator is transparent uniform liquid, and the density is 1.15g/cm3～1.2g/cm3The method can greatly reduce the alkali-aggregate reaction risk of the concrete, and all the raw materials do not contain chloride ions, fluoride ions and sodium ions, so that the corrosion of the raw materials on the reinforced concrete is reduced.
The invention has good adaptability to cement, can provide good quick-hardening early-strength performance to moderate heat cement which is widely applied in water quantity industry, and meets the construction requirement of sprayed concrete. The mixing amount of the ordinary Portland cement can be properly reduced, and the requirements of related projects can be met.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The liquid alkali-free fluoride-free chlorine-free concrete accelerator comprises the following components in percentage by mass: 45% of aluminum sulfate, 1.5% of modifying regulator, 3.5% of diethanolamine, 2% of magnesium sulfate, 1% of calcium formate, 1% of urea and the balance of water, wherein the sum of the components is 100%.
The preparation method comprises the following steps:
weighing the raw materials in proportion, adding water into a reaction kettle, heating while stirring, and gradually adding aluminum sulfate; after the temperature is controlled at 55 ℃, magnesium sulfate and calcium formate are sequentially added according to the measurement every 5min, and the mixture is continuously stirred and reacts for 1.5 h; and naturally cooling to normal temperature, adding urea, a modification regulator and diethanolamine, stirring for 20min, and controlling the pH of the accelerator solution to be 2.5 to obtain the finished product of the liquid concrete accelerator, wherein the performance test results are shown in Table 1.
The preparation method of the modified regulator comprises the following steps: weighing 2mol of diethanolamine, 1mol of triethanolamine, 1mol of tartaric acid, 1mol of glycerol and 0.5mol of ethyl acetate in sequence, adding the materials into a reactor in sequence, wherein the time interval between each feeding is 5-10 min, adding 0.05mol of concentrated sulfuric acid as a catalyst, and stirring for reacting for about half an hour.
Example 2
The liquid alkali-free fluoride-free chlorine-free concrete accelerator comprises the following components in percentage by mass: 50.5 percent of aluminum sulfate, 1.8 percent of modifying regulator, 4 percent of diethanolamine, 2.2 percent of magnesium sulfate, 2.5 percent of calcium formate, 1.5 percent of urea and the balance of water, wherein the sum of the components is 100 percent.
The preparation method comprises the following steps:
weighing the raw materials in proportion, adding water into a reaction kettle, heating while stirring, and gradually adding aluminum sulfate; after the temperature is controlled at 60 ℃, magnesium sulfate and calcium formate are sequentially added every 7min according to the measurement, and the mixture is continuously stirred and reacts for 1.8 h; and naturally cooling to normal temperature, adding urea, a modification regulator and diethanolamine, stirring for 25min, and controlling the pH of the accelerator solution to be 2.7 to obtain the finished product of the liquid concrete accelerator, wherein the performance test results are shown in Table 1.
The preparation method of the modified regulator comprises the following steps: weighing 2mol of diethanolamine, 1mol of triethanolamine, 1mol of tartaric acid, 1mol of glycerol and 0.5mol of ethyl acetate in sequence, adding the materials into a reactor in sequence, wherein the time interval between each feeding is 5-10 min, adding 0.05mol of concentrated sulfuric acid as a catalyst, and stirring for reacting for about half an hour.
Example 3
The liquid alkali-free fluoride-free chlorine-free concrete accelerator comprises the following components in percentage by mass: 55% of aluminum sulfate, 2.5% of a modification regulator, 5% of diethanolamine, 2.5% of magnesium sulfate, 3% of calcium formate, 2% of urea and the balance of water, wherein the sum of the components is 100%.
The preparation method comprises the following steps:
weighing the raw materials in proportion, adding water into a reaction kettle, heating while stirring, and gradually adding aluminum sulfate; after the temperature is controlled at 65 ℃, sequentially adding magnesium sulfate and calcium formate every 8min, and continuously stirring for reacting for 2 h; and naturally cooling to normal temperature, adding urea, a modification regulator and diethanolamine, stirring for 30min, and controlling the pH value of the accelerator solution to be 3 to obtain the finished product of the liquid concrete accelerator, wherein the performance test results are shown in Table 1.
The preparation method of the modified regulator comprises the following steps: weighing 2mol of diethanolamine, 1mol of triethanolamine, 1mol of tartaric acid, 1mol of glycerol and 0.5mol of ethyl acetate in sequence, adding the materials into a reactor in sequence, wherein the time interval between each feeding is 5-10 min, adding 0.05mol of concentrated sulfuric acid as a catalyst, and stirring for reacting for about half an hour.
Table 1 results of performance testing of examples
Remarking:1#TABLE 1 detection of Cement as reference Cement
2#The stability in Table 1 means the maximum time without delamination and precipitation at room temperature
Meanwhile, the performances and states of accelerator products corresponding to different combinations of the regulating agents are compared, and the comparison result is as follows: the product stability and adaptability of the different combinations of the regulators (TA tartrate, Glycerol, TEA triethanolamine, EA acetate, DEA diethanolamine) and the corresponding accelerator products in Table 2 (8 cements common in the market are selected for the accelerator adaptability: benchmark, Huarun, Xilin, Red lion, Huaxin, Heixiao, southwest and Kotelin cements, specification: PO.42.5).
TABLE 2
As can be seen from the data in Table 2, code 9 is a concrete accelerator using a self-made long-chain type modifier which is significantly improved in adaptability and stability. The modifier No. 9 was used as a modifying modifier in the above examples.
While the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope of the disclosure.
Claims (6)
1. An alkali-free fluoride-free chlorine-free liquid concrete accelerator is characterized in that: the raw materials consist of aluminum sulfate, a modified regulator, magnesium sulfate, calcium formate, urea and water; the raw materials comprise the following components in percentage by mass:
wherein the modifying and regulating agent is prepared by stirring and reacting diethanol amine, triethanolamine, tartaric acid, glycerol, ethyl acetate and concentrated sulfuric acid.
2. The alkali-free, fluorine-free and chlorine-free liquid concrete accelerator as claimed in claim 1, wherein: the quantity ratio of diethanolamine, triethanolamine, tartaric acid, glycerol, ethyl acetate and concentrated sulfuric acid in the modifying and regulating agent is 2:1:1:1:0.5: 0.05.
3. The alkali-free, fluorine-free and chlorine-free liquid concrete accelerator as claimed in claim 1, wherein: the raw materials comprise the following components in percentage by mass:
4. the alkali-free, fluorine-free and chlorine-free liquid concrete accelerator as claimed in any one of claims 1 to 3, wherein: the preparation method of the concrete accelerator comprises the following steps: weighing the raw materials in proportion, adding water into a reaction kettle, heating while stirring, and gradually adding aluminum sulfate; after the temperature is controlled to be 55-65 ℃, sequentially adding magnesium sulfate and calcium formate every 5-8 min, and continuously stirring for reacting for 1.5-2 h; and naturally cooling to normal temperature, adding urea, a modification regulator and diethanolamine, stirring for 20-30 min, and controlling the pH of the accelerator solution to be 2.5-3 to obtain the finished product of the liquid concrete accelerator.
5. The alkali-free, fluorine-free and chlorine-free liquid concrete accelerator as claimed in claim 4, wherein: the preparation method of the modified regulator comprises the following steps: weighing the raw materials according to the proportion, feeding the raw materials while stirring according to the sequence of diethanolamine, triethanolamine, tartaric acid, glycerol, ethyl acetate and concentrated sulfuric acid, wherein the interval time of each feeding is 5-10 min, stirring the raw materials for 25-35 min after all the raw materials are added, and controlling the reaction temperature to be 65-70 ℃ to prepare the mixed long-chain type modifying regulator.
6. The alkali-free, fluorine-free and chlorine-free liquid concrete accelerator as claimed in claim 4, wherein: the stirring speed is 300 r/min-500 r/min.
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| CN202111577792.5A CN114057422B (en) | 2021-12-22 | 2021-12-22 | Alkali-free fluorine-free chlorine-free liquid concrete accelerator and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024062805A1 (en) * | 2022-09-20 | 2024-03-28 | デンカ株式会社 | Liquid quick-setting agent and shotcrete |
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