CN115872657A - Anti-freezing low-alkali accelerator and preparation method thereof - Google Patents
Anti-freezing low-alkali accelerator and preparation method thereof Download PDFInfo
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- CN115872657A CN115872657A CN202211618491.7A CN202211618491A CN115872657A CN 115872657 A CN115872657 A CN 115872657A CN 202211618491 A CN202211618491 A CN 202211618491A CN 115872657 A CN115872657 A CN 115872657A
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- 238000007710 freezing Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
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- 238000003756 stirring Methods 0.000 claims abstract description 66
- 239000011734 sodium Substances 0.000 claims abstract description 42
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 42
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- 239000000725 suspension Substances 0.000 claims abstract description 35
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 23
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- 239000003381 stabilizer Substances 0.000 claims abstract description 10
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- 230000002528 anti-freeze Effects 0.000 claims description 10
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention belongs to the technical field of concrete admixtures, and particularly discloses an anti-freezing low-alkali setting accelerator and a preparation method thereof, wherein the low-alkali setting accelerator comprises the following components in parts by weight: the preparation method comprises the following steps: step 1: stirring sodium metaaluminate with a small amount of water uniformly to prepare a sodium metaaluminate solution; and 2, step: preparing modified aluminum hydroxide suspension; and 3, step 3: adding iron-free aluminum sulfate and simultaneously adding a stabilizer; and 4, step 4: then adding a complexing agent and a complexing agent for stirring; and 5: dropwise adding the modified thickening agent, keeping the temperature, stirring for 2h, and taking out of the pot. The antifreezing low-alkali accelerator has stronger antifreezing capability, does not have freezing phenomenon after being frozen for 30 days in the environment of 10 ℃ below zero, has low price which is about 1/2-1/4 of the price of the alkali-free accelerator, and has higher use value.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to an anti-freezing low-alkali accelerator and a preparation method thereof.
Background
The accelerator is a chemical additive capable of enabling cement or concrete to be rapidly solidified and hardened, and is widely applied to projects such as highways, tunnels, revetments and the like. With the updating of accelerating agents, liquid alkali-free (low) accelerating agents become the mainstream of accelerating agent markets in recent years.
The liquid accelerator is divided into an alkali accelerator and a non (low) alkali accelerator. The alkali accelerator has the defects of high alkali content, high alkali corrosion, large concrete shrinkage, low later strength, damage to the health of constructors and the like, and is listed as a rejected material by housing and urban and rural construction departments at present. Compared with the alkali accelerating agent, the low-alkali or alkali-free accelerating agent has less harm to human bodies, and the concrete doped with the low-alkali or alkali-free accelerating agent has high retention rate of later strength and no influence on durability.
In recent years, researchers at home and abroad synthesize some alkali-free liquid accelerators, but the synthesis process of the alkali-free accelerator is complex, the synthesis period is long, and the price is high, so that the research on the accelerator gradually develops towards the low-alkali accelerator.
Although various performance indexes of the traditional low-alkali setting accelerator meet the requirements, most of the low-alkali setting accelerators can be frozen when winter comes, so that the low-alkali setting accelerators cannot be used for sprayed concrete constructed in winter, and the preparation of the anti-freezing low-alkali setting accelerator has great significance for the construction of sprayed concrete in winter.
Disclosure of Invention
In order to solve the technical problems, the invention provides an anti-freezing low-alkali accelerator and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the invention relates to an anti-freezing low-alkali accelerator which comprises the following components in percentage by mass: 40-50% of iron-free aluminum sulfate, 5-10% of modified aluminum hydroxide, 1-3% of sodium metaaluminate, 3-10% of complexing agent, 5-10% of stabilizing agent, 1.5-2.5% of complexing agent, 0.5-1.5% of modified thickening agent and the balance of water.
The preparation method of the anti-freezing low-alkali accelerator comprises the following steps:
step 1: stirring sodium metaaluminate with small amount of water to obtain sodium metaaluminate solution;
and 2, step: taking aluminum hydroxide as a matrix, and carrying out physical and chemical modification on the aluminum hydroxide for 30min at the temperature of 85-90 ℃ to obtain a modified aluminum hydroxide suspension;
and step 3: reducing the temperature in the step 2 to 65-70 ℃, keeping the stirring state, slowly adding the iron-free aluminum sulfate, and simultaneously adding the stabilizer, wherein the stirring time is 25-30 min, and the stirring speed is not less than 200r/min;
and 4, step 4: then adding a complexing agent and a complexing agent, and stirring for 20min;
and 5: dropwise adding the modified thickening agent, keeping the temperature, stirring for 2h, and taking out of the pot.
Preferably: the preparation of the modified aluminum hydroxide suspension in the step 2 is to perform physical modification and chemical modification on aluminum hydroxide, wherein the physical modification specifically comprises the following steps: pouring 500g of aluminum hydroxide into a charging barrel, adding 2.5g of triethanolamine for grinding to obtain aluminum hydroxide ultrafine powder, and adding 1% by mass of sodium phosphate into the aluminum hydroxide ultrafine powder for chemical modification, wherein the specific steps are as follows: putting the aluminum hydroxide ultrafine powder into a glass reaction vessel, pouring water generated during synthesis of the accelerator, adjusting the temperature of the glass reaction vessel to 85-90 ℃, and reacting at high temperature for 30min to obtain the modified aluminum hydroxide suspension.
Preferably: the preparation method of the modified thickener in the step 5 comprises the following steps: firstly, preparing a small monomer solution containing half of the total amount of small monomers, acrylic acid and a small monomer solution containing a group amide group, placing the small monomer solution in a four-neck flask, heating the small monomer solution to 40 +/-2 ℃, then preparing the other half of small monomers into a solution A, preparing a chain transfer agent, namely the thioethanolamine and an initiator, namely vitamin C into a solution B, and adding hydrogen peroxide (H) after the temperature in the four-neck flask is stabilized to 40 +/-2 DEG C 2 O 2 ) Beginning to dropwise add the solution A and the solution B after 10min, wherein the solution A is dropwise added at a constant speed for 60min, the solution B is dropwise added at a constant speed for 90min, the temperature is kept at 40 +/-2 ℃ after dropwise addition is finished, and the solution is continuously stirred for 60min till the reaction is finished to obtain the modified thickened solutionAnd (3) preparing.
Preferably, the following components: the iron-free aluminum sulfate is white powdery ultrafine powder with the particle size of 0-2 mm, and the proportion of aluminum oxide is more than or equal to 16 percent.
Preferably, the following components: the addition amount of the modified aluminum hydroxide is 5-10% of the solid content of the accelerator.
Preferably: the complexing agent is one or the mixture of two of sodium fluoride and sodium aluminate.
Preferably, the following components: the stabilizer is one or more of ethylene glycol, diethanol amine and triethanolamine.
Preferably, the following components: the complexing agent is one or more of oxalic acid, phosphoric acid and silicic acid.
The invention has the beneficial effects that:
(1) The efficient anti-freezing low-alkali accelerator provided by the invention has strong anti-freezing capacity, does not have freezing phenomenon after being frozen for 30 days in an environment of 10 ℃ below zero, and has low price which is about 1/2-1/4 of the price of an alkali-free accelerator.
(2) The high-efficiency anti-freezing low-alkali accelerator provided by the invention has strong adaptability with cement, shows good accelerating effect and early strengthening effect with portland cement, ordinary portland cement and reference cement, and has high use value.
(3) The invention can solve a series of problems caused by other accelerators, has the advantages of greenness, safety, good stability, good durability, good mechanical property, low rebound rate and the like, and improves the market share of the product.
Drawings
FIG. 1 is a product diagram of example 3 of the present invention.
FIG. 2 is a diagram of a comparative example 6 of the present invention.
FIG. 3 is a state diagram after freezing in embodiment 4.
Fig. 4 is a state diagram after comparative example 4 was frozen.
Detailed Description
In the following description, for purposes of explanation, numerous implementation details are set forth in order to provide a thorough understanding of the embodiments of the invention. It should be understood, however, that these implementation details are not to be interpreted as limiting the invention. That is, in some embodiments of the invention, such implementation details are not necessary.
The invention relates to a high-efficiency anti-freezing liquid low-alkali setting accelerator which comprises the following raw material components in percentage by mass based on the total weight of the raw materials:
40 to 50 percent of iron-free aluminum sulfate
5 to 10 percent of modified aluminum hydroxide
Sodium metaaluminate 1-3%
3 to 10 percent of complexing agent
5 to 10 percent of stabilizer
1.5 to 2.5 percent of complexing agent
0.5 to 1.5 percent of modified thickening agent
The balance of water, the total weight of which is up to 100%.
The modified aluminum hydroxide method mainly comprises two aspects of modification, on one hand, a vibrating superfine grinding mixing roll is used for carrying out superfine grinding on aluminum hydroxide for 10min, 0.5% triethanolamine is added as a grinding aid, and the grinding efficiency is high; on the other hand, 1 percent of dispersant sodium phosphate is utilized to carry out surface modification on the aluminum hydroxide, the modification time is 30min, and the temperature is 85-90 ℃.
The complexing agent is one or more of sodium fluoride and sodium aluminate which are mixed in any proportion.
The stabilizer is one or more of ethylene glycol, diethanol amine and triethanol amine mixed in any proportion.
The complexing agent is one or more of oxalic acid, phosphoric acid and silicic acid mixed in any proportion.
The modified thickener is mainly modified by introducing an amide group into a polyacrylic thickener.
The preparation method of the anti-freezing low-alkali accelerator comprises the following steps:
step 1: sodium metaaluminate is stirred evenly by a small amount of water to prepare sodium metaaluminate solution.
Step 2: the method comprises the following steps of (1) taking aluminum hydroxide as a matrix, carrying out physical and chemical modification on the aluminum hydroxide, wherein the physical modification is mainly realized by improving the specific surface area of the aluminum hydroxide, pouring 500g of the aluminum hydroxide into a charging barrel, adding 2.5g of triethanolamine, and grinding to obtain aluminum hydroxide ultrafine powder; secondly, 1 percent of sodium phosphate is added into the aluminum hydroxide ultrafine powder for chemical modification, and the specific modification steps are as follows: at the initial stage of the synthesis of the low-alkali accelerating agent, a proper amount of aluminum hydroxide ultrafine powder is taken and placed in a glass reaction vessel, water during the synthesis of the accelerating agent is poured, the temperature of a water bath is adjusted to 85-90 ℃, and the high-temperature reaction is carried out for 30min, so as to obtain the modified aluminum hydroxide suspension, wherein, when the aluminum hydroxide ultrafine powder is added, the rotating speed of a stirrer is maintained at 60-100 r/min for stirring, the temperature is reduced to 65-70 ℃, and after aluminum sulfate and other raw materials are added, the rotating speed is adjusted to 200r/min.
And step 3: reducing the temperature in the step 2 to 65-70 ℃, keeping the stirring state, slowly adding the iron-free aluminum sulfate, and simultaneously adding the stabilizer, wherein the stirring time is 25-30 min, and the stirring speed is not less than 200r/min;
and 4, step 4: then adding a complexing agent and a complexing agent, and stirring for 20min;
and 5: dropwise adding a modified thickening agent, keeping the temperature, stirring for 2h, taking out of the pot, wherein the modified thickening agent is prepared by introducing an amide group into a polyacrylic acid thickening agent for modification by a molecular design method to prepare a carboxyl group (-COOH) and an amide group (-CNH) 2 O) ratio of 1: firstly, preparing a proper amount of acrylic acid containing half of total amount of small monomers and small monomer solution containing amide groups, placing the small monomer solution in a four-neck flask, heating the small monomer solution to 40 +/-2 ℃, then preparing the other half of small monomers into solution A, preparing a chain transfer agent, namely the thioethanolamine and an initiator, namely vitamin C into solution B, and adding hydrogen peroxide (H) after the temperature in the four-neck flask is stabilized to 40 +/-2 DEG C 2 O 2 ) And after 10min, beginning to dropwise add the solution A and the solution B, wherein the solution A is dropwise added at a constant speed for 60min, the solution B is dropwise added at a constant speed for 90min, and after the dropwise addition is finished, continuously keeping the temperature at 40 +/-2 ℃ and continuously stirring for 60min until the reaction is finished to obtain the modified thickener.
Example one
The embodiment provides a high-efficiency anti-freezing low-alkali accelerator and a preparation method thereof, wherein the preparation method comprises the following steps
(1) The efficient anti-freezing low-alkali setting accelerator comprises the following components in percentage by weight:
| components | Ratio of occupation of |
| Iron- |
40% |
| Modified aluminium hydroxide | 5% |
| Sodium metaaluminate | 1.5% |
| |
10% |
| Diethanolamine: triethanolamine (1 | 8% |
| Phosphoric acid | 2.5% |
| Modified thickening agent | 1.5% |
| Water (W) | 31.5% |
(2) Putting 25g of modified aluminum hydroxide and 50g of water into a glass reaction container, adding 0.25g of sodium phosphate, and stirring at the high temperature of 85-90 ℃ for 30min to prepare modified aluminum hydroxide suspension;
(3) Stirring 7.5g of sodium metaaluminate and 20g of water uniformly for later use, weighing 20g of diethanolamine, 20g of triethanolamine and 50g of water, and stirring uniformly for later use;
(4) Sequentially adding 200g of iron-free aluminum sulfate, a sodium metaaluminate solution, 50g of sodium fluoride, 12.5g of phosphoric acid and 7.5g of a modified thickening agent into the modified aluminum hydroxide suspension, and simultaneously adding 37.5g of water into the modified aluminum hydroxide suspension for stirring, wherein the stirring temperature is 65-70 ℃;
(5) After all the materials are put in, the water bath kettle is closed after the materials are stirred for 2 hours under the condition of the temperature of 65-70 ℃, and the low-alkali accelerating agent is obtained after the materials are cooled to the normal temperature.
Example 2
The embodiment provides a high-efficiency anti-freezing low-alkali accelerator and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) The high-efficiency anti-freezing low-alkali setting accelerator comprises the following components in percentage by weight:
| components | Ratio of occupation of |
| Iron- |
40% |
| |
10% |
| Sodium metaaluminate | 3.5% |
| Sodium fluoride | 8% |
| Diethanolamine: triethanolamine (1 | 6% |
| Phosphoric acid | 1.5% |
| Modified thickening agent | 0.5% |
| Water (W) | 30.5% |
(2) Putting 50g of modified aluminum hydroxide and 50g of water into a glass reaction vessel, adding 0.5g of sodium phosphate, and stirring at the high temperature of 85-90 ℃ for 30min to prepare modified aluminum hydroxide suspension;
(3) Stirring 17.5g of sodium metaaluminate and 20g of water uniformly for later use, weighing 15g of diethanolamine, 15g of triethanolamine and 50g of water, and stirring uniformly for later use;
(4) Sequentially adding 200g of iron-free aluminum sulfate, a sodium metaaluminate solution, 40g of sodium fluoride, 7.5g of phosphoric acid and 2.5g of a modified thickening agent into the modified aluminum hydroxide suspension, and simultaneously adding 32.5g of water into the modified aluminum hydroxide suspension for stirring, wherein the stirring temperature is 65-70 ℃;
(5) After all the materials are put in, stirring for 2 hours at the temperature of 65-70 ℃, closing the water bath kettle, and cooling to normal temperature to obtain the low-alkali accelerating agent.
Example 3
The embodiment provides a high-efficiency anti-freezing low-alkali accelerator and a preparation method thereof, and the method comprises the following steps:
(1) The efficient anti-freezing low-alkali setting accelerator comprises the following components in percentage by weight:
| components | Ratio of the ingredients |
| Iron-free aluminium sulphate | 45% |
| Modified aluminium hydroxide | 5% |
| Sodium metaaluminate | 2.5% |
| Sodium fluoride | 5% |
| Diethanolamine: triethanolamine (1 | 8% |
| Phosphoric acid | 2.5% |
| Modified thickening agent | 1.5% |
| Water (W) | 30.5% |
(2) Putting 25g of modified aluminum hydroxide and 50g of water into a glass reaction vessel, adding 0.25g of sodium phosphate, and stirring at the high temperature of 85-90 ℃ for 30min to prepare a modified aluminum hydroxide suspension.
(3) 12.5g of sodium metaaluminate and 20g of water are stirred uniformly for standby. Weighing 20g of diethanolamine, 20g of triethanolamine and 50g of water, and uniformly stirring for later use.
(4) 225g of iron-free aluminum sulfate, sodium metaaluminate solution, 25g of sodium fluoride, 12.5g of phosphoric acid and 7.5g of modified thickening agent are sequentially added into the modified aluminum hydroxide suspension, and 32.5g of water is added and stirred at the temperature of 65-70 ℃.
(5) After all the materials are put in, stirring for 2 hours at the temperature of 65-70 ℃, closing the water bath kettle, and cooling to normal temperature to obtain the low-alkali accelerating agent, as shown in figure 1.
Example 4
The embodiment provides a high-efficiency anti-freezing low-alkali accelerator and a preparation method thereof, and the method comprises the following steps:
(1) The high-efficiency anti-freezing low-alkali setting accelerator comprises the following components in percentage by weight:
| components | Ratio of occupation of |
| Iron-free aluminium sulphate | 45% |
| |
10% |
| Sodium metaaluminate | 2.5% |
| Sodium fluoride | 3% |
| Diethanolamine: triethanolamine (1 | 6% |
| Phosphoric acid | 1.5% |
| Modified thickening agent | 0.5% |
| Water (W) | 31.5% |
(2) Putting 50g of modified aluminum hydroxide and 50g of water into a glass reaction container, adding 0.5g of sodium phosphate, and stirring at the high temperature of 85-90 ℃ for 30min to prepare modified aluminum hydroxide suspension;
(3) Uniformly stirring 12.5g of sodium metaaluminate and 20g of water for later use, weighing 15g of diethanolamine, 15g of triethanolamine and 50g of water, and uniformly stirring for later use;
(4) Adding 225g of iron-free aluminum sulfate, sodium metaaluminate solution, 15g of sodium fluoride, 7.5g of phosphoric acid and 2.5g of modified thickening agent into the modified aluminum hydroxide suspension in sequence, adding 37.5g of water into the modified aluminum hydroxide suspension, and stirring at the temperature of 65-70 ℃;
(5) After all the materials are put in, stirring for 2 hours at the temperature of 65-70 ℃, closing the water bath kettle, and cooling to normal temperature to obtain the low-alkali accelerating agent.
Example 5
The embodiment provides a high-efficiency anti-freezing low-alkali accelerator and a preparation method thereof, and the method comprises the following steps:
(1) The efficient anti-freezing low-alkali setting accelerator comprises the following components in percentage by weight:
| components | Ratio of occupation of |
| Iron- |
50% |
| Modified aluminium hydroxide | 5% |
| Sodium metaaluminate | 3.5% |
| Sodium fluoride | 5% |
| Diethanolamine: triethanolamine (1 | 8% |
| Phosphoric acid | 2.5% |
| Modified thickening agent | 1.5% |
| Water (W) | 24.5% |
(2) Putting 25g of modified aluminum hydroxide and 50g of water into a glass reaction container, adding 0.25g of sodium phosphate, and stirring at the high temperature of 85-90 ℃ for 30min to prepare modified aluminum hydroxide suspension;
(3) Stirring 17.5g of sodium metaaluminate and 20g of water uniformly for later use, and weighing 20g of diethanolamine, 20g of triethanolamine and 50g of water and stirring uniformly for later use;
(4) Adding 250g of iron-free aluminum sulfate, sodium metaaluminate solution, 25g of sodium fluoride, 12.5g of phosphoric acid and 7.5g of modified thickening agent into the modified aluminum hydroxide suspension in sequence, supplementing 2.5g of water, adding into the modified aluminum hydroxide suspension, and stirring at the temperature of 65-70 ℃;
(5) After all the materials are put in, stirring for 2 hours at the temperature of 65-70 ℃, closing the water bath kettle, and cooling to normal temperature to obtain the low-alkali accelerating agent.
Example 6
The embodiment provides a high-efficiency anti-freezing low-alkali accelerator and a preparation method thereof, and the method comprises the following steps:
(1) The efficient anti-freezing low-alkali setting accelerator comprises the following components in percentage by weight:
| components | Ratio of occupation of |
| Iron- |
50% |
| |
10% |
| Sodium metaaluminate | 1.5% |
| Sodium fluoride | 3% |
| Diethanolamine: triethanolamine (1 | 6% |
| Phosphoric acid | 1.5% |
| Modified thickening agent | 0.5% |
| Water (W) | 27.5% |
(2) Putting 50g of modified aluminum hydroxide and 50g of water into a glass reaction container, adding 0.5g of sodium phosphate, and stirring at the high temperature of 85-90 ℃ for 30min to prepare modified aluminum hydroxide suspension;
(3) Stirring 7.5g of sodium metaaluminate and 20g of water uniformly for later use, weighing 15g of diethanolamine, 15g of triethanolamine and 50g of water, and stirring uniformly for later use;
(4) Adding 250g of iron-free aluminum sulfate, sodium metaaluminate solution, 15g of sodium fluoride, 7.5g of phosphoric acid and 2.5g of modified thickening agent into the modified aluminum hydroxide suspension in sequence, adding 37.5g of water into the modified aluminum hydroxide suspension, and stirring at the temperature of 65-70 ℃;
(5) After all the materials are put in, stirring for 2 hours at the temperature of 65-70 ℃, closing the water bath kettle, and cooling to normal temperature to obtain the low-alkali accelerating agent.
Comparative example 1
Referring to patent CN113045236A, the antifreeze early strength alkali-free liquid accelerator prepared in example 3 comprises the following steps:
(1) Mixing 40g of aluminum sulfate, 3g of potassium fluosilicate, 3g of triisopropanolamine, 5g of diethylenetriamine and 47g of water, and preserving heat for 2 hours at the temperature of 75 ℃; cooling to 45 deg.C, adding 2g modified hydrated magnesium silicate, and mixing to obtain coagulation regulating component;
(2) Mixing 15g of glutamic acid, 15g of alanine, 15g of aspartic acid and 55g of water, and stirring for 1 hour at the temperature of 45 ℃ to obtain the required solubilizing component;
(3) Mixing 3g of lithium nitrate, 15g of beryllium nitrate, 12g of bismuth nitrate, 5g of methanesulfonic acid, 5g of benzenesulfonic acid and 60g of water, and stirring at the temperature of 45 ℃ for 1 hour to obtain the required anti-freezing early-strength component;
(4) And (3) sequentially adding 4g of solubilizing component and 16g of anti-freezing early-strength component into 80g of coagulation regulating component at the temperature of 45 ℃, uniformly mixing and cooling to obtain the anti-freezing early-strength alkali-free liquid accelerator.
Comparative example 2
Referring to patent CN109399999B, the early strength type low alkali liquid accelerator prepared in example 2 comprises the following steps:
(1) Adding water into a water bath container and heating to 60-70 ℃;
(2) While stirring, 50g of sodium fluoride and 40g of aluminum isopropoxide were added to 135g of water in this order;
(3) Slowly dripping 30g of triethanolamine maleate by using a constant flow pump, wherein the dripping time is finished within 1-1.5 h;
(4) Keeping the constant temperature state, adding 225g of aluminum sulfate, and continuously stirring until the aluminum sulfate is completely dissolved;
(5) And transferring the solution to a laboratory high-speed shearing emulsifying machine, adding 15g of mild wheel rubber and 5g of polydimethylsiloxane, starting the high-speed shearing emulsifying machine, adjusting the rotating speed to 3000-5000 r/min, and emulsifying for 0.5-1 h to obtain the early-strength low-alkali liquid accelerator.
Comparative example 3
The preparation method of the high-efficiency anti-freezing low-alkali accelerator comprises the following steps:
(1) The low-alkali accelerator comprises the following components in percentage by weight:
| components | Ratio of the ingredients |
| Iron- |
40% |
| |
10% |
| Sodium metaaluminate | 3.5% |
| Sodium fluoride | 8% |
| Diethanolamine: triethanolamine (1 | 6% |
| Phosphoric acid | 1.5% |
| Ordinary thickening agent | 0.5% |
| Water (W) | 31.5% |
(2) 50g of common aluminum hydroxide and 50g of water are put into a glass reaction vessel and stirred for 30min at a high temperature of between 85 and 90 ℃ to prepare an aluminum hydroxide suspension.
(3) 17.5g of sodium metaaluminate and 20g of water are stirred uniformly for standby. Weighing 15g of diethanolamine, 15g of triethanolamine and 50g of water, and uniformly stirring for later use.
(4) 200g of iron-free aluminum sulfate, sodium metaaluminate solution, 40g of sodium fluoride, 7.5g of phosphoric acid and 2.5g of common thickening agent are sequentially added into the aluminum hydroxide suspension, and 37.5g of water is added into the aluminum hydroxide suspension for stirring at the temperature of 65-70 ℃.
(5) After all the materials are put in, stirring for 2 hours at the temperature of 65-70 ℃, closing the water bath kettle, and cooling to normal temperature to obtain the low-alkali accelerating agent.
Comparative example 4
The preparation method of the high-efficiency anti-freezing low-alkali accelerator comprises the following steps:
(1) The low-alkali accelerator comprises the following components in percentage by weight:
| components | Ratio of occupation of |
| Iron-free aluminium sulphate | 45% |
| Ordinary aluminium hydroxide | 5% |
| Sodium metaaluminate | 2.5% |
| Sodium fluoride | 5% |
| Diethanolamine: triethanolamine (1 | 8% |
| Phosphoric acid | 2.5% |
| Ordinary thickening agent | 1.5% |
| Water (W) | 30.5% |
(2) 25g of common aluminum hydroxide and 50g of water are put into a glass reaction vessel and stirred for 30min at the high temperature of 85-90 ℃ to prepare modified aluminum hydroxide suspension.
(3) 12.5g of sodium metaaluminate and 20g of water are stirred uniformly for standby. Weighing 20g of diethanolamine, 20g of triethanolamine and 50g of water, and uniformly stirring for later use.
(4) 225g of iron-free aluminum sulfate, sodium metaaluminate solution, 25g of sodium fluoride, 12.5g of phosphoric acid and 7.5g of common thickening agent are sequentially added into the aluminum hydroxide suspension, and 32.5g of water is added and stirred at the temperature of 65-70 ℃.
(5) After all the materials are put in, stirring for 2 hours at the temperature of 65-70 ℃, closing the water bath kettle, and cooling to normal temperature to obtain the low-alkali accelerating agent.
Comparative example 5
The preparation method of the high-efficiency anti-freezing low-alkali accelerator comprises the following steps:
(1) The low-alkali accelerator comprises the following components in percentage by weight:
| components | Ratio of occupation of |
| Iron-free aluminium sulphate | 45% |
| |
10% |
| Sodium metaaluminate | 2.5% |
| Sodium fluoride | 3% |
| Diethanolamine: triethanolamine (1 | 6% |
| Phosphoric acid | 1.5% |
| Ordinary thickening agent | 0.5% |
| Water (W) | 31.5% |
(2) 50g of modified aluminum hydroxide and 50g of water are put into a glass reaction vessel, 0.5g of sodium phosphate is added, and the mixture is stirred for 30min at the high temperature of 85-90 ℃ to prepare modified aluminum hydroxide suspension.
(3) 12.5g of sodium metaaluminate and 20g of water are stirred uniformly for standby. Weighing 15g of diethanolamine, 15g of triethanolamine and 50g of water, and uniformly stirring for later use.
(4) 225g of iron-free aluminum sulfate, a sodium metaaluminate solution, 15g of sodium fluoride, 7.5g of phosphoric acid and 2.5g of a common thickener are sequentially added into the aluminum hydroxide suspension, and 37.5g of water is added into the suspension and stirred at the temperature of 65-70 ℃.
(5) After all the materials are put in, stirring for 2 hours at the temperature of 65-70 ℃, closing the water bath kettle, and cooling to normal temperature to obtain the low-alkali accelerating agent.
Comparative example 6
The preparation method of the high-efficiency anti-freezing low-alkali accelerator comprises the following steps:
(1) The low-alkali accelerator comprises the following components in percentage by weight:
| components | Ratio of occupation of |
| Iron- |
50% |
| Ordinary aluminium hydroxide | 5% |
| Sodium metaaluminate | 3.5% |
| Sodium fluoride | 5% |
| Diethanolamine: triethanolamine (1 | 8% |
| Phosphoric acid | 2.5% |
| Ordinary thickening agent | 1.5% |
| Water (W) | 24.5% |
(2) 25g of common aluminum hydroxide and 50g of water are put into a glass reaction vessel and stirred for 30min at the high temperature of 85-90 ℃ to prepare modified aluminum hydroxide suspension.
(3) 17.5g of sodium metaaluminate and 20g of water are stirred uniformly for standby. Weighing 20g of diethanolamine, 20g of triethanolamine and 50g of water, and uniformly stirring for later use.
(4) 250g of iron-free aluminum sulfate, sodium metaaluminate solution, 25g of sodium fluoride, 12.5g of phosphoric acid and 7.5g of common thickening agent are sequentially added into the aluminum hydroxide suspension, and then 2.5g of water is added and stirred, wherein the stirring temperature is 65-70 ℃.
(5) After all the materials are put in, stirring for 2 hours at the temperature of 65-70 ℃, closing the water bath kettle, and cooling to normal temperature to obtain the low-alkali accelerating agent, as shown in figure 2.
The performance test results of the accelerating agents of the examples and the comparative examples are shown in a table 1.
TABLE 1 test results of accelerator performance of examples and comparative examples
As can be seen from Table 1, the low-alkali setting accelerator of the invention has better setting time and strength than other low-alkali setting accelerators, because the setting accelerator contains a large amount of aluminum ions, and after the modified aluminum hydroxide is added, the dissolution of the aluminum ions is increased, thus promoting the setting of cement. The low-alkali accelerator can generate columnar calcium silicate hydrate gel and AFt crystals at the early stage of cement hydration, the crystals can quickly nucleate and grow up along with the prolonging of time, an interwoven and staggered network structure can be formed, and more Al is provided by adding the modified aluminum hydroxide 3+ ，Al 3+ Incorporating a large amount of OH - . This reduces C 3 And an electric double layer structure is formed on the surface of the S, so that the cement is rapidly coagulated. The components without modified aluminum hydroxide in the table have stability problems, and after the modified thickener is added, a plurality of carboxyl groups on a molecular structure chain of the modified thickener can present a curled random shape under an acidic or neutral condition, so that the state is stable and the viscosity is low. After sodium metaaluminate is added into the system, the copolymer on the modified thickener particles is subjected to alkali dissolution, electrostatic repulsion is generated, a network structure is formed, the flow of water molecules is hindered, and the stability of the low-alkali accelerating agent is ensured.
Table 2 shows the results of the evaluation of the anti-freeze properties of the accelerators in the examples and the comparative examples
Referring to FIG. 3, the frozen state diagram of example 4 and the frozen state diagram of FIG. 4, the states of the examples in Table 2 are not frozen because the modified aluminum hydroxide provides more aluminum ions, and the modified aluminum hydroxide provides a solubilizing effect after the alcohol is introduced, and the more aluminum ions increase the anti-freezing performance of the accelerator and enhance the low-temperature stability of the accelerator. According to various tests, the frost resistance of the low-alkali accelerating agent is compared with that of an alkali-free accelerating agent, although the frost resistance of the low-alkali accelerating agent is not frozen at minus 10 ℃, the freezing phenomenon appears when the low-alkali accelerating agent is placed at minus 20 ℃, and the frost resistance of the low-alkali accelerating agent is weaker than that of the alkali-free accelerating agent.
The efficient antifreezing low-alkali setting accelerator provided by the invention has strong antifreezing capability, does not have freezing phenomenon after being frozen for 30 days in an environment of 10 ℃ below zero, and has low price which is about 1/2-1/4 of the price of an alkali-free setting accelerator.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (9)
1. An anti-freezing low-alkali accelerator is characterized in that: the low-alkali accelerator comprises the following components in percentage by mass: 40-50% of iron-free aluminum sulfate, 5-10% of modified aluminum hydroxide, 1-3% of sodium metaaluminate, 3-10% of complexing agent, 5-10% of stabilizing agent, 1.5-2.5% of complexing agent, 0.5-1.5% of modified thickening agent and the balance of water.
2. A method for preparing the freeze-resistant low-alkali accelerator according to claim 1, wherein: the preparation method comprises the following steps:
step 1: uniformly stirring sodium metaaluminate with water to prepare a sodium metaaluminate solution;
step 2: taking aluminum hydroxide as a matrix, and carrying out physical and chemical modification on the aluminum hydroxide for 30min at the temperature of 85-90 ℃ to obtain a modified aluminum hydroxide suspension;
and step 3: reducing the temperature in the step 2 to 65-70 ℃, keeping the stirring state, slowly adding the iron-free aluminum sulfate, and simultaneously adding the stabilizer, wherein the stirring time is 25-30 min, and the stirring speed is not less than 200r/min;
and 4, step 4: then adding a complexing agent and a complexing agent, and stirring for 20min;
and 5: dropwise adding the modified thickening agent, keeping the temperature, stirring for 2h, and taking out of the pot.
3. The preparation method of the antifreeze low-alkali accelerator as claimed in claim 2, wherein the antifreeze low-alkali accelerator comprises the following steps: the preparation of the modified aluminum hydroxide suspension in the step 2 is to perform physical modification and chemical modification on aluminum hydroxide, wherein the physical modification specifically comprises the following steps: pouring 500g of aluminum hydroxide into a charging barrel, adding 2.5g of triethanolamine for grinding to obtain aluminum hydroxide ultrafine powder, and adding 1% by mass of sodium phosphate into the aluminum hydroxide ultrafine powder for chemical modification, wherein the specific steps are as follows: putting the aluminum hydroxide ultrafine powder into a glass reaction vessel, pouring water generated during synthesis of the accelerator, adjusting the temperature of the glass reaction vessel to 85-90 ℃, and reacting at high temperature for 30min to obtain the modified aluminum hydroxide suspension.
4. The preparation method of the antifreeze low-alkali accelerator as claimed in claim 2, wherein the antifreeze low-alkali accelerator comprises the following steps: the preparation method of the modified thickener in the step 5 comprises the following steps: firstly, preparing a small monomer solution containing half of the total amount of small monomers, acrylic acid and a small monomer solution containing a group amide group, placing the small monomer solution in a four-neck flask, heating the small monomer solution to 40 +/-2 ℃, then preparing the other half of small monomers into a solution A, preparing a chain transfer agent, namely the thioethanolamine and an initiator, namely vitamin C into a solution B, and adding hydrogen peroxide (H) after the temperature in the four-neck flask is stabilized to 40 +/-2 DEG C 2 O 2 ) And after 10min, beginning to dropwise add the solution A and the solution B, wherein the solution A is dropwise added at a constant speed for 60min, the solution B is dropwise added at a constant speed for 90min, and after the dropwise addition is finished, continuously keeping the temperature at 40 +/-2 ℃ and continuously stirring for 60min until the reaction is finished to obtain the modified thickener.
5. The preparation method of the freeze-resistant low-alkali accelerator as claimed in claim 2, characterized in that: the iron-free aluminum sulfate is white powdery superfine powder with the particle size of 0-2 mm, and the proportion of aluminum oxide is more than or equal to 16 percent.
6. The preparation method of the antifreeze low-alkali accelerator as claimed in claim 2, wherein the antifreeze low-alkali accelerator comprises the following steps: the addition amount of the modified aluminum hydroxide is 5-10% of the solid content of the anti-freezing low-alkali accelerator.
7. The preparation method of the antifreeze low-alkali accelerator as claimed in claim 2, wherein the antifreeze low-alkali accelerator comprises the following steps: the complexing agent is one or a mixture of sodium fluoride and sodium aluminate.
8. The preparation method of the freeze-resistant low-alkali accelerator as claimed in claim 2, characterized in that: the stabilizer is one or a mixture of more of ethylene glycol, diethanol amine and triethanolamine.
9. The preparation method of the freeze-resistant low-alkali accelerator as claimed in claim 2, characterized in that: the complexing agent is one or a mixture of oxalic acid, phosphoric acid and silicic acid.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936913A (en) * | 2014-03-14 | 2014-07-23 | 中交四航工程研究院有限公司 | Thickener used for self-compact concrete, preparation method thereof, and self-compact concrete using thickener |
| CN104140806A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Modified acrylamide polymer thickening agent and preparation method thereof |
| CN104761171A (en) * | 2015-04-24 | 2015-07-08 | 张萍 | Liquid accelerator and preparation method thereof |
| CN108178553A (en) * | 2018-01-23 | 2018-06-19 | 云南森博混凝土外加剂有限公司 | It is a kind of low admittedly containing accelerator and preparation method thereof |
| CN108440995A (en) * | 2018-01-15 | 2018-08-24 | 大连亚泰科技新材料股份有限公司 | A kind of method that wet method prepares modified micro-nano flame retardant of magnesium hydroxide |
| CN109437654A (en) * | 2018-12-11 | 2019-03-08 | 湖北腾辰科技股份有限公司 | A kind of preparation method of enhanced alkali-free liquid accelerator |
-
2022
- 2022-12-15 CN CN202211618491.7A patent/CN115872657B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140806A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Modified acrylamide polymer thickening agent and preparation method thereof |
| CN103936913A (en) * | 2014-03-14 | 2014-07-23 | 中交四航工程研究院有限公司 | Thickener used for self-compact concrete, preparation method thereof, and self-compact concrete using thickener |
| CN104761171A (en) * | 2015-04-24 | 2015-07-08 | 张萍 | Liquid accelerator and preparation method thereof |
| CN108440995A (en) * | 2018-01-15 | 2018-08-24 | 大连亚泰科技新材料股份有限公司 | A kind of method that wet method prepares modified micro-nano flame retardant of magnesium hydroxide |
| CN108178553A (en) * | 2018-01-23 | 2018-06-19 | 云南森博混凝土外加剂有限公司 | It is a kind of low admittedly containing accelerator and preparation method thereof |
| CN109437654A (en) * | 2018-12-11 | 2019-03-08 | 湖北腾辰科技股份有限公司 | A kind of preparation method of enhanced alkali-free liquid accelerator |
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