CN109293269B - Preparation method of early-strength alkali-free liquid accelerator - Google Patents
Preparation method of early-strength alkali-free liquid accelerator Download PDFInfo
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- CN109293269B CN109293269B CN201811492517.1A CN201811492517A CN109293269B CN 109293269 B CN109293269 B CN 109293269B CN 201811492517 A CN201811492517 A CN 201811492517A CN 109293269 B CN109293269 B CN 109293269B
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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
Abstract
The invention discloses a preparation method of an early-strength alkali-free liquid accelerator, belonging to the technical field of building materials. The accelerator is prepared from the following components in percentage by mass: 55-70% of aluminum sulfate, 5-10% of magnesium sulfate, 5-10% of modified alcohol amine, 2-5% of organic acid, 1-3% of stabilizer, 1-3% of EDTA, 0.5-2% of calcium formate and the balance of water. The method specifically comprises the following steps: (1) preparing modified alcohol amine; (2): and (3) preparing the early-strength alkali-free liquid accelerator. The early-strength alkali-free liquid accelerator prepared by the invention can be used in the shotcrete industry, has alkali content less than 1%, a stabilization period of more than 3 months, 1d compressive strength of 19.93MPa and 28d compressive strength loss, is an early-strength alkali-free liquid accelerator, and can be widely applied to initial construction and first-aid repair of various building projects.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to an early-strength alkali-free liquid accelerator and a preparation method thereof.
Background
The accelerating agent is an additive used in cement concrete to make the cement concrete quickly set and harden. The concrete wet spraying construction process is popularized from 90 s in the 20 th century in China, and the key problems of ensuring the quality of sprayed finished products and reasonable construction process are solved. The precondition guarantee is to develop the accelerating agent with excellent performance and good accelerating effect.
At present, the quick-setting admixture is divided into powder and liquid, wherein the powder quick-setting admixture is gradually replaced by the liquid quick-setting admixture due to poor construction operation conditions, damage to health of constructors and uncontrollable construction process. The liquid accelerator mainly comprises two main types of low alkali and alkali-free in the field application nowadays. The low-alkali accelerator mainly comprises NaAlO2、NaSiO4And a composite product; the alkali-free liquid accelerator mainly contains Al2(SO4)3And a composite product. The traditional aluminate low-alkali liquid accelerator has single component, and the cement is quickly condensed mainly by promoting the hydration of aluminate minerals in the cement,the adaptability to cement with more mineral admixture is poor.
In addition, some patents are named as alkali-free setting accelerators, but the alkali introduced into the formula is often more than 1% from related patents disclosed at present, such as the invention patent (application number: 2016108141346) disclosed by Shanxi Kentungshi environmental protection science and technology corporation, but the alkali content in the actual formula can reach 11.1% at most although the patent is named as the alkali-free setting accelerator; the invention patent (application number: 2017101015775) disclosed by Shanxi Kaiwei Wei science and technology Limited company is named as alkali-free accelerator, but the alkali content in the actual formula can reach 13.3 percent at most. On one hand, the higher alkali content in the concrete accelerator causes corrosion damage to constructors and damages to human health, and on the other hand, the alkali-aggregate reaction of the concrete can be caused, so that the later strength and durability of the concrete are reduced. The invention patent (application number: 2016110965096) disclosed by Changan university provides an accelerator with low early strength, which easily influences the normal construction of sprayed concrete. In conclusion, the development of the alkali-free liquid accelerator which is really alkali-free and has excellent performance is of great significance.
Disclosure of Invention
The aluminum sulfate alkali-free liquid accelerator is used as a main body, and the modified alcohol amine organic micromolecules and the EDTA are used as coordination agents to promote the coordination combination of aluminum ions and functional groups and enhance the stability of the aluminum sulfate alkali-free liquid accelerator in a high-concentration solution. Meanwhile, calcium formate is used for making up the defect of low early strength of the quick-setting accelerator caused by quick setting, and the early-strength alkali-free liquid quick-setting accelerator with excellent performance and the preparation method thereof are prepared. The quick-setting agent can shorten the quick-setting time and ensure the early strength to be qualified, and has the advantages of good adaptability, simple preparation, practicality and energy conservation. In order to realize the purpose of the invention, the adopted technical scheme is as follows:
a preparation method of an early strength alkali-free liquid accelerator comprises the following steps:
(1) the preparation method of the modified alcohol amine comprises the following steps: adding alcohol amine, amine organic matters and a catalyst into a 250ml four-mouth bottle provided with a mechanical stirring device, a circulating condensing device and a thermometer according to the molar ratio of 1:2-3:0.0034-0.01, reacting for 1-2.5h at 65-90 ℃, adding 2-3mol of organic acid into the obtained mixed solution, and reacting for 0.5-1h to obtain modified alcohol amine;
(2) preparing an early strength type alkali-free liquid accelerator: firstly, placing aluminum sulfate, magnesium sulfate and organic acid in a three-neck flask, adding deionized water, and stirring for 1-2 hours at the temperature of 60-90 ℃ in a constant-temperature water bath at 300-400 r/min to obtain accelerator mother liquor; and (2) stirring at 300r/min-400r/min in a constant-temperature water bath at 60-75 ℃, adding the modified alcohol amine obtained in the step (1) into the accelerator mother liquor, continuously stirring for 30min, adding calcium formate, stirring for 30min, adding EDTA after the stirring is finished, keeping the temperature at 65-70 ℃, stirring for 40min, cooling to room temperature, adding a stabilizer, and stirring at 200r/min-300r/min for 20min to obtain the early-strength alkali-free liquid accelerator.
In the step (1), the alcohol amine is one or more of monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine and diethanolisopropanolamine.
In the step (1), the amine organic matter is one or more of ethylenediamine, p-phenylenediamine, 1, 4-butanediamine, neopentylene diamine, decamethylene diamine or 2-methyl pentamethylene diamine.
The catalyst in the step (1) is one or more of p-toluenesulfonic acid, anhydrous sodium acetate, aluminum chloride or zinc chloride.
The organic acid is one or more of oxalic acid, propionic acid, salicylic acid or benzoic acid.
The stabilizer is one or more of citric acid, glycine and alanine.
The aluminum sulfate is of industrial grade, wherein the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the purity is more than or equal to 98 percent.
The calcium formate is analytically pure, and the purity is more than or equal to 99.5 percent; the EDTA is analytically pure, and the purity is more than or equal to 99.5 percent.
The early-strength alkali-free liquid accelerator prepared by the method is prepared from the following raw materials in percentage by mass: 55-70% of aluminum sulfate, 5-10% of magnesium sulfate, 5-10% of modified alcohol amine, 2-5% of organic acid, 1-3% of stabilizer, 1-3% of EDTA, 0.5-2% of calcium formate and the balance of deionized water.
The aluminum sulfate and the magnesium sulfate used in the invention are mixed as the main components of the accelerator, wherein the introduced magnesium ions can be preferentially combined with OH in the cement hydration process-Formation of Mg (OH)2Become nucleation particles, and accelerate the hydration process of cement. The chemical imbalance caused by the high content of aluminum ions leads to gypsum and C3A is easier to dissolve, and promotes the generation of a large amount of early ettringite, thereby achieving the effect of quick setting. The calcium formate and the modified alcohol amine can effectively improve the coagulation accelerating and early strength performance of the accelerator.
Compared with the prior art, the invention has the following beneficial effects: (1) the alkali-free liquid accelerator provided by the invention is added into a sprayed cement composition according to a conventional method, the early strength of concrete is rapidly developed, the later strength is not influenced, and the defect that the later strength of concrete is obviously reduced due to the large amount of the traditional alkali accelerator is overcome; (2) the alkali-free liquid accelerator provided by the invention greatly reduces the possibility of generating alkali-aggregate reaction; (3) the alkali-free accelerator provided by the invention has good adaptability with cement, and meets the requirements of sprayed concrete construction on different brands of cement.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
A preparation method of an early strength alkali-free liquid accelerator comprises the following steps:
(1) the preparation method of the modified alcohol amine comprises the following steps: adding alcohol amine, amine organic matters and a catalyst into a 250ml four-mouth bottle provided with a mechanical stirring device, a circulating condensing device and a thermometer, wherein the mol ratio of the alcohol amine to the amine organic matters is 1: 3: 0.005, reacting for 1h at 65 ℃, and adding 2mol of organic acid into the obtained mixed solution to react for 0.5h to obtain modified alcohol amine;
(2) preparing an early strength type alkali-free liquid accelerator: putting 60g of aluminum sulfate, 6g of magnesium sulfate and 6g of organic acid into a three-neck flask, adding 30g of deionized water, and stirring for 1.5 hours at 400r/min in a constant-temperature water bath at 80 ℃ to obtain accelerator mother liquor; stirring at 350r/min in a constant-temperature water bath at 65 ℃, adding 6g of modified alcohol amine obtained in the step (1) into the accelerator mother liquor, continuously stirring for 30min, adding 1.5g of calcium formate, stirring for 30min, adding 2g of EDTA after the stirring is finished, keeping the temperature and stirring for 40min at 65 ℃, cooling to room temperature, adding 2g of stabilizer, and stirring for 20min at 300r/min to obtain the early-strength alkali-free liquid accelerator.
In the step (1), the alcohol amine is diethanolamine.
In the step (1), the amine organic substance is ethylenediamine.
The catalyst in the step (1) is p-toluenesulfonic acid.
The organic acid is oxalic acid.
The stabilizing agent is citric acid.
The aluminum sulfate is of industrial grade, wherein the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the purity is more than or equal to 98 percent.
The calcium formate is analytically pure, and the purity is more than or equal to 99.5 percent; the EDTA is analytically pure, and the purity is more than or equal to 99.5 percent.
An early strength type alkali-free liquid accelerator is prepared from the following raw materials in percentage by mass: 55% of aluminum sulfate, 5% of magnesium sulfate, 5% of modified alcohol amine, 2% of organic acid, 1% of stabilizer, 1% of EDTA, 1% of calcium formate and the balance of deionized water.
Example 2
A preparation method of an early strength alkali-free liquid accelerator comprises the following steps:
(1) the preparation method of the modified alcohol amine comprises the following steps: adding alcohol amine, amine organic matters and a catalyst into a 250ml four-mouth bottle provided with a mechanical stirring device, a circulating condensing device and a thermometer, wherein the mol ratio of the alcohol amine to the amine organic matters is 1: 2.5: 0.0045. reacting at 65 ℃ for 1.5h, and adding 3mol of organic acid into the obtained mixed solution to react for 45min to obtain modified alcohol amine;
(2) preparing an early strength type alkali-free liquid accelerator: firstly, placing 75g of aluminum sulfate, 8g of magnesium sulfate and 5g of organic acid in a three-neck flask, then adding 19g of deionized water, and stirring for 2 hours at 400r/min in a constant-temperature water bath at 80 ℃ to obtain accelerator mother liquor; stirring at 400r/min in a constant-temperature water bath at 65 ℃, adding 10g of modified alcohol amine obtained in the step (1) into the accelerator mother liquor, continuously stirring for 30min, adding 2g of calcium formate, stirring for 30min, adding 2.5g of EDTA after the stirring is finished, keeping the temperature and stirring for 40min at 65 ℃, cooling to room temperature, adding 3g of stabilizer, and stirring for 20min at 300r/min to obtain the early-strength alkali-free liquid accelerator.
In the step (1), the alcohol amine is triisopropanolamine.
In the step (1), the amine organic substance is ethylenediamine.
The catalyst in the step (1) is p-toluenesulfonic acid.
The organic acid is oxalic acid.
The stabilizing agent is citric acid.
The aluminum sulfate is of industrial grade, wherein the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the purity is more than or equal to 98 percent.
The calcium formate is analytically pure, and the purity is more than or equal to 99.5 percent; the EDTA is analytically pure, and the purity is more than or equal to 99.5 percent.
An early strength type alkali-free liquid accelerator is prepared from the following raw materials in percentage by mass: 60% of aluminum sulfate, 6% of magnesium sulfate, 8% of modified alcohol amine, 4% of organic acid, 2% of stabilizing agent, 2% of EDTA, 1% of calcium formate and the balance of deionized water.
Example 3
A preparation method of an early strength alkali-free liquid accelerator comprises the following steps:
(1) the preparation method of the modified alcohol amine comprises the following steps: adding alcohol amine, amine organic matters and a catalyst into a 250ml four-mouth bottle provided with a mechanical stirring device, a circulating condensing device and a thermometer, wherein the mol ratio of the alcohol amine to the amine organic matters is 1: 3: 0.01. reacting at 75 ℃ for 1h, and adding 3mol of organic acid into the obtained mixed solution to react for 45min to obtain modified alcohol amine;
(2) preparing an early strength type alkali-free liquid accelerator: putting 85g of aluminum sulfate, 10g of magnesium sulfate and 5g of organic acid into a three-neck flask, adding 20g of deionized water, and stirring for 2 hours at 400r/min in a constant-temperature water bath at 85 ℃ to obtain accelerator mother liquor; stirring at 400r/min in a constant-temperature water bath at 70 ℃, adding 10g of modified alcohol amine obtained in the step (1) into a mother liquor of the accelerating agent, continuously stirring for 30min, adding 3g of calcium formate, stirring for 30min, adding 3g of EDTA after the stirring is finished, keeping the temperature at 65 ℃, stirring for 40min, cooling to room temperature, adding 5g of stabilizer, and stirring at 300r/min for 20min to obtain the early-strength alkali-free liquid accelerating agent.
In the step (1), the alcohol amine is triethanolamine.
In the step (1), the amine organic substance is 1, 4-butanediamine.
The catalyst in the step (1) is anhydrous sodium acetate.
The organic acid is benzoic acid.
The stabilizer is glycine.
The aluminum sulfate is of industrial grade, wherein the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the purity is more than or equal to 98 percent.
The calcium formate is analytically pure, and the purity is more than or equal to 99.5 percent; the EDTA is analytically pure, and the purity is more than or equal to 99.5 percent.
An early strength type alkali-free liquid accelerator is prepared from the following raw materials in percentage by mass: 60% of aluminum sulfate, 7% of magnesium sulfate, 7% of modified alcohol amine, 3% of organic acid, 3% of stabilizing agent, 2% of EDTA, 2% of calcium formate and the balance of deionized water.
Example 4
A preparation method of an early strength alkali-free liquid accelerator comprises the following steps:
(1) the preparation method of the modified alcohol amine comprises the following steps: adding alcohol amine, amine organic matters and a catalyst into a 250ml four-mouth bottle provided with a mechanical stirring device, a circulating condensing device and a thermometer, wherein the mol ratio of the alcohol amine to the amine organic matters is 1: 2: 0.01. reacting for 2h at 80 ℃, and adding 2.5mol of organic acid into the obtained mixed solution to react for 45min to obtain modified alcohol amine;
(2) preparing an early strength type alkali-free liquid accelerator: putting 78g of aluminum sulfate, 6g of magnesium sulfate and 5g of organic acid into a three-neck flask, adding 19g of deionized water, and stirring for 2 hours at 400r/min in a constant-temperature water bath at 85 ℃ to obtain accelerator mother liquor; stirring at 400r/min in a constant-temperature water bath at 70 ℃, adding 8g of modified alcohol amine obtained in the step (1) into a mother liquor of the accelerating agent, continuously stirring for 30min, adding 0.5g of calcium formate, stirring for 30min, adding 1.5g of EDTAs after the stirring, keeping the temperature and stirring for 40min at 65 ℃, cooling to room temperature, adding 3g of stabilizing agent, and stirring for 20min at 300r/min to obtain the early-strength alkali-free liquid accelerating agent.
In the step (1), the alcohol amine is triethanolamine.
In the step (1), the amine organic matter is p-phenylenediamine.
The catalyst in the step (1) is anhydrous sodium acetate.
The organic acid is salicylic acid.
The stabilizer is glycine.
The aluminum sulfate is of industrial grade, wherein the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the purity is more than or equal to 98 percent.
The calcium formate is analytically pure, and the purity is more than or equal to 99.5 percent; the EDTA is analytically pure, and the purity is more than or equal to 99.5 percent.
An early strength type alkali-free liquid accelerator is prepared from the following raw materials in percentage by mass: 64% of aluminum sulfate, 5% of magnesium sulfate, 6% of modified alcohol amine, 4% of organic acid, 2% of stabilizing agent, 1% of EDTA, 0.5% of calcium formate and the balance of deionized water.
Example 5
A preparation method of an early strength alkali-free liquid accelerator comprises the following steps:
(1) the preparation method of the modified alcohol amine comprises the following steps: adding alcohol amine, amine organic matters and a catalyst into a 250ml four-mouth bottle provided with a mechanical stirring device, a circulating condensing device and a thermometer, wherein the mol ratio of the alcohol amine to the amine organic matters is 1: 2: 0.0035. after reacting for 1h at 72 ℃, adding 2.5mol of organic acid into the obtained mixed solution to react for 1h to obtain modified alcohol amine;
(2) preparing an early strength type alkali-free liquid accelerator: putting 90g of aluminum sulfate, 10g of magnesium sulfate and 6g of organic acid into a three-neck flask, adding 10g of deionized water, and stirring for 1.5 hours at 400r/min in a constant-temperature water bath at 85 ℃ to obtain accelerator mother liquor; stirring at 400r/min in a constant-temperature water bath at 65 ℃, adding 8g of modified alcohol amine obtained in the step (1) into accelerator mother liquor, continuously stirring for 30min, adding 2.5g of calcium formate, stirring for 30min, adding EDTA4g after the stirring is finished, keeping the temperature at 65 ℃ and stirring for 40min, cooling to room temperature, adding 4g of stabilizer, and stirring at 300r/min for 20min to obtain the early-strength alkali-free liquid accelerator.
In the step (1), the alcohol amine is diethanol monoisopropanolamine.
In the step (1), the amine organic matter is decamethylene diamine.
The catalyst in the step (1) is aluminum chloride.
The organic acid is oxalic acid.
The stabilizer is alanine.
The aluminum sulfate is of industrial grade, wherein the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the purity is more than or equal to 98 percent.
The calcium formate is analytically pure, and the purity is more than or equal to 99.5 percent; the EDTA is analytically pure, and the purity is more than or equal to 99.5 percent.
An early strength type alkali-free liquid accelerator is prepared from the following raw materials in percentage by mass: 67% of aluminum sulfate, 7% of magnesium sulfate, 6% of modified alcohol amine, 5% of organic acid, 3% of stabilizing agent, 3% of EDTA, 2% of calcium formate and the balance of deionized water.
Example 6
A preparation method of an early strength alkali-free liquid accelerator comprises the following steps:
(1) the preparation method of the modified alcohol amine comprises the following steps: adding alcohol amine, amine organic matters and a catalyst into a 250ml four-mouth bottle provided with a mechanical stirring device, a circulating condensing device and a thermometer, wherein the mol ratio of the alcohol amine to the amine organic matters is 1: 3: 0.003. after reacting for 15h at 80 ℃, adding 2.5mol of organic acid into the obtained mixed solution to react for 1h to obtain modified alcohol amine;
(2) preparing an early strength type alkali-free liquid accelerator: placing 80g of aluminum sulfate, 8g of magnesium sulfate and 5g of organic acid in a three-neck flask, adding 20g of deionized water, and stirring for 2 hours at 400r/min in a constant-temperature water bath at 85 ℃ to obtain accelerator mother liquor; stirring at 400r/min in a constant-temperature water bath at 65 ℃, adding 8g of modified alcohol amine obtained in the step (1) into the accelerator mother liquor, continuously stirring for 30min, adding 2g of calcium formate, stirring for 30min, adding EDTA3g after the stirring is finished, keeping the temperature and stirring for 40min at 65 ℃, cooling to room temperature, adding 3g of stabilizer, and stirring for 20min at 300r/min to obtain the early-strength alkali-free liquid accelerator.
In the step (1), the alcohol amine is diethanolamine.
In the step (1), the amine organic matter is 2-methyl pentanediamine.
The catalyst in the step (1) is zinc chloride.
The organic acid is benzoic acid.
The stabilizer is alanine.
The aluminum sulfate is of industrial grade, wherein the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the purity is more than or equal to 98 percent.
The calcium formate is analytically pure, and the purity is more than or equal to 99.5 percent; the EDTA is analytically pure, and the purity is more than or equal to 99.5 percent.
An early strength type alkali-free liquid accelerator is prepared from the following raw materials in percentage by mass: 62% of aluminum sulfate, 6% of magnesium sulfate, 6% of modified alcohol amine, 4% of organic acid, 2% of stabilizing agent, 2% of EDTA, 1% of calcium formate and the balance of deionized water.
Example 7
A preparation method of an early strength alkali-free liquid accelerator comprises the following steps:
(1) the preparation method of the modified alcohol amine comprises the following steps: adding alcohol amine, amine organic matters and a catalyst into a 250ml four-mouth bottle provided with a mechanical stirring device, a circulating condensing device and a thermometer, wherein the mol ratio of the alcohol amine to the amine organic matters is 1: 2.5: 0.0034. after reacting for 2h at 90 ℃, adding 2mol of organic acid into the obtained mixed solution to react for 0.5-1h to obtain modified alcohol amine;
(2) preparing an early strength type alkali-free liquid accelerator: putting 90g of aluminum sulfate, 10g of magnesium sulfate and 5g of organic acid into a three-neck flask, adding 6g of deionized water, and stirring for 2 hours at 300r/min in a 90-DEG C constant-temperature water bath to obtain accelerator mother liquor; and (2) stirring at 300r/min in a 75 ℃ constant-temperature water bath, adding 10g of modified alcohol amine obtained in the step (1) into the accelerator mother liquor, continuously stirring for 30min, adding 2g of calcium formate, stirring for 30min, adding EDTA3g after the stirring is finished, keeping the temperature and stirring for 40min at 70 ℃, cooling to room temperature, adding 3g of stabilizer, and stirring for 20min at 200r/min to obtain the early-strength alkali-free liquid accelerator.
In the step (1), the alcohol amine is triethanolamine.
In the step (1), the amine organic matter is 2-methyl pentanediamine.
The catalyst in the step (1) is zinc chloride.
The organic acid is benzoic acid.
The stabilizer is glycine.
The aluminum sulfate is of industrial grade, wherein the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the purity is more than or equal to 98 percent.
The calcium formate is analytically pure, and the purity is more than or equal to 99.5 percent; the EDTA is analytically pure, and the purity is more than or equal to 99.5 percent.
An early strength type alkali-free liquid accelerator is prepared from the following raw materials in percentage by mass: 70% of aluminum sulfate, 7% of magnesium sulfate, 7% of modified alcohol amine, 3% of organic acid, 2% of stabilizing agent, 2% of EDTA, 1% of calcium formate and the balance of deionized water.
Test example
Cement paste setting time and cement mortar strength test:
the liquid setting accelerators obtained in examples 1 to 7 were added to the cement paste in amounts of 4% and 6% by weight of the cement. The cement paste setting time and the cement mortar strength test are carried out according to the requirements of Chinese building material industry standard JC477-2005 accelerator for sprayed concrete. The test results are shown in Table 1.
TABLE 1 Cement paste setting time and Cement mortar Strength test
As can be seen from the data in the table 1, the prepared liquid accelerator has obvious accelerating effect, greatly shortens the setting time, has higher strength at 1d and small strength loss at 28d, completely meets the requirements of the field, and achieves the expected effect.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Claims (8)
1. The preparation method of the early-strength alkali-free liquid accelerator is characterized by comprising the following steps of:
(1) the preparation method of the modified alcohol amine comprises the following steps: adding alcohol amine, amine organic matters and a catalyst into a 250ml four-mouth bottle provided with a mechanical stirring device, a circulating condensing device and a thermometer according to the molar ratio of 1:2-3:0.0034-0.01, reacting for 1-2.5h at 65-90 ℃, adding 2-3mol of organic acid into the obtained mixed solution, and reacting for 0.5-1h to obtain modified alcohol amine;
(2) preparing an early strength type alkali-free liquid accelerator: placing aluminum sulfate, magnesium sulfate and organic acid in a three-neck flask, adding deionized water, and stirring for 1-2 hours at the temperature of 60-90 ℃ in a constant-temperature water bath at 300-400 r/min to obtain accelerator mother liquor; stirring at 300r/min-400r/min in a constant-temperature water bath at 60-75 ℃, adding the modified alcohol amine obtained in the step (1) into the accelerator mother liquor, continuously stirring for 30min, adding calcium formate, stirring for 30min, adding EDTA after the stirring is finished, keeping the temperature at 65-70 ℃, stirring for 40min, cooling to room temperature, adding a stabilizer, and stirring at 200r/min-300r/min for 20min to obtain the early-strength alkali-free liquid accelerator;
the catalyst in the step (1) is one or more of p-toluenesulfonic acid, anhydrous sodium acetate, aluminum chloride or zinc chloride; the stabilizer is one or more of citric acid, glycine and alanine.
2. The method for preparing the early-strength alkali-free liquid accelerator as claimed in claim 1, wherein the alcohol amine in the step (1) is one or more of monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine and diethanolisopropanolamine.
3. The preparation method of the early strength alkali-free liquid accelerator as claimed in claim 1, wherein the amine organic compound in step (1) is one or more of ethylenediamine, p-phenylenediamine, 1, 4-butanediamine, neopentyldiamine, decamethylenediamine or 2-methylpentylenediamine.
4. The preparation method of the early strength alkali-free liquid accelerator as claimed in claim 1, wherein the organic acid is one or more of oxalic acid, propionic acid, salicylic acid or benzoic acid.
5. The preparation method of the early-strength alkali-free liquid accelerator as claimed in claim 1, wherein the aluminum sulfate is industrial grade, and the mass fraction of aluminum oxide is more than or equal to 16.00%.
6. The preparation method of the early strength alkali-free liquid accelerator as claimed in claim 1, wherein the magnesium sulfate is of industrial grade and has a purity of not less than 98%.
7. The preparation method of the early strength alkali-free liquid accelerator as claimed in claim 1, wherein the calcium formate is analytically pure, and the purity is more than or equal to 99.5%; the EDTA is analytically pure, and the purity is more than or equal to 99.5 percent.
8. An accelerator prepared by the preparation method of the early strength alkali-free liquid accelerator as claimed in any one of claims 1 to 7, which is characterized by being prepared from the following raw materials in percentage by mass: 55-70% of aluminum sulfate, 5-10% of magnesium sulfate, 5-10% of modified alcohol amine, 2-5% of organic acid, 1-3% of stabilizer, 1-3% of EDTA, 0.5-2% of calcium formate and the balance of deionized water.
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| CN110330255B (en) * | 2019-07-02 | 2021-08-31 | 安徽海螺新材料科技有限公司 | Coagulation-promoting liquid grinding aid and preparation method thereof |
| CN113087441B (en) * | 2021-03-05 | 2023-04-18 | 山西佳维新材料股份有限公司 | Fluoride-free liquid alkali-free accelerator and preparation method and application thereof |
| CN113480226B (en) * | 2021-08-02 | 2022-12-13 | 江西立晶新材料科技有限公司 | Liquid alkali-free accelerator and preparation method and application thereof |
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| CN102923988A (en) * | 2012-11-29 | 2013-02-13 | 北京冶建特种材料有限公司 | Liquid alkali-free chloride-free accelerating agent as well as methods for preparing and using same |
| JP6131063B2 (en) * | 2013-02-06 | 2017-05-17 | デンカ株式会社 | Liquid quick setting agent, cement composition using the same, and spraying method |
| CN105174796B (en) * | 2015-10-16 | 2018-02-09 | 广州大广高速公路有限公司 | A kind of alkali-free liquid concrete accelerator and preparation method thereof |
| CN105776939B (en) * | 2016-03-15 | 2017-10-13 | 江苏中铁奥莱特新材料股份有限公司 | A kind of low resilience, enhancing, the preparation method of Liquid Low-Alkali Shotcrete Admixture |
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