CN115057650A - Chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator and preparation method thereof - Google Patents
Chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator and preparation method thereof Download PDFInfo
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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
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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 provides a chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator and a preparation method thereof, and the accelerator comprises the following raw materials: 45-55 parts of high-concentration polyaluminum sulfate, 5-8 parts of a composite early strength agent, 2-3.5 parts of an insulating component, 1.5-2.5 parts of a composite rust inhibitor, 1-2 parts of a reinforcing agent, 0.3-0.6 part of a thickening agent, 0.25-0.75 part of an acidity regulator and 30-45 parts of deionized water. According to the invention, the red mud is taken as an experimental raw material to successfully prepare the high-concentration polyaluminium sulfate, so that the accelerating effect of the accelerator is ensured, the introduction of fluorine-containing components is avoided, and the resource utilization of the aluminum industrial waste is effectively realized. The accelerator disclosed by the invention can effectively improve the chloride ion permeability resistance of sprayed concrete, improves the stability of a suspension type liquid accelerator, and can meet various technical requirements of GB/T35159-2017 accelerator for sprayed concrete on the liquid accelerator.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a fluoride-free alkali-free liquid accelerator resistant to chloride ion permeation and a preparation method thereof.
Background
Saline-alkali soil has serious harm to reinforced concrete, so that stricter requirements on the performance of sprayed concrete in tunnel engineering construction are met.
In combination with the research results at the present stage, the accelerator has a remarkable correlation with the performance of the sprayed concrete. In the aspect of functions, the accelerator can accelerate the setting and hardening of the sprayed concrete, can prevent the sprayed concrete from falling off due to gravity, reduces the rebound loss, and improves the early strength of the concrete to a certain extent. In terms of classification, the quick-setting admixture is generally classified into a powder quick-setting admixture and a liquid quick-setting admixture, but the powder quick-setting admixture is gradually replaced by the liquid quick-setting admixture in consideration of the defects of poor construction environment, high resilience, low construction efficiency and the like of the conventional dry spraying process. The liquid setting accelerator for wet spraying process mainly comprises an alkaline setting accelerator and an alkali-free setting accelerator. The alkali accelerator has high alkali content, so that on one hand, the health of constructors is easily damaged, and on the other hand, alkali aggregate reaction is initiated, so that the later strength and durability of the sprayed concrete are seriously and negatively influenced. Therefore, the alkali-free liquid accelerator gradually becomes an important trend for the development of the accelerator industry by comprehensively considering various factors such as the mechanical property of the sprayed concrete, the construction process and the like.
From the requirements of national standards (GB/T35159-2017) for accelerators for sprayed concrete, the content of chloride ions in the alkali-free liquid accelerator should be lower than 0.01 percent, which avoids introducing chloride ions into the sprayed concrete in the process of externally mixing the accelerator. However, from the practical situation of tunnel engineering construction, the coverage area of saline-alkali soil in western regions is wide, and the content of chloride in natural environment is relatively high, so that a large amount of chloride ions permeate into the sprayed concrete during the service period of the tunnel, and the corrosion behavior of the surface of the steel bar is caused. Meanwhile, the shotcrete is easy to generate a large amount of pore structures inside due to short setting and hardening time, and the pore structures usually help chloride ions to rapidly spread inside the shotcrete, so that the damage to the service performance of the steel bars is further aggravated.
The patent with publication number CN111333362A, which is published on 26.6.2020, discloses a low-dosage high-early-strength alkali-free liquid accelerator and a preparation method thereof, wherein the alkali-free liquid accelerator is prepared from the following raw materials: modified aluminum sulfate, industrial aluminum hydroxide, fluosilicic acid, alcohol amine, hydrated magnesium silicate, hydrated calcium silicate, lithium nitrate, hydroxyethyl cellulose and the like. The accelerator has good accelerating effect, can effectively shorten the setting time of concrete, and also has a plurality of excellent performances of low doping amount, high early strength, large retention rate of later strength and the like. Meanwhile, the preparation method of the alkali-free liquid accelerator mainly comprises four process steps: firstly, preparing modified aluminum sulfate by grinding and sieving; secondly, stirring industrial aluminum hydroxide, fluosilicic acid and water at normal temperature for 20-30 min to prepare a fluorine-aluminum complex solution; then, sequentially adding water, modified aluminum sulfate and an organic cosolvent into a reaction container (the dropwise adding time is 45-60 min) to prepare a solution A; and finally, slowly adding the fluorine-aluminum complex solution, stirring at normal temperature for 20-30 min, and sequentially adding a pH regulator, a stabilizer, a viscosity regulator and a composite early strength agent to prepare the alkali-free liquid accelerator.
The publication number CN109231871A published in 2019, 1 month and 18 days also discloses a low-dosage high-performance alkali-free and chlorine-free liquid accelerator and a preparation method thereof, wherein the raw material components and the mass fractions of the components are as follows: 30-60 parts of aluminum sulfate, 0-20 parts of magnesium sulfate, 0.5-2.0 parts of precipitated hydrous magnesium silicate, 0.5-2.0 parts of magnesium oxide, 1-3 parts of magnesium fluosilicate, 1-3 parts of alcohol amine, 0.5-1.5 parts of high molecular polymer, 0.2-1.0 part of stabilizer, 5-40 parts of fluorine-aluminum complex solution and 30-50 parts of water. The accelerator also has a plurality of excellent performances such as low mixing amount, high early strength, high later strength retention rate and the like.
The attention of the prior art is mainly focused on the accelerating effect of the accelerating agent, the influence on the concrete strength and the like, and the corrosion action of chloride salt on steel bars in the natural environment is not deeply studied, so that the chloride ion permeability resistance of sprayed concrete is relatively poor. Meanwhile, in order to reduce the mixing amount of the accelerator, the technology introduces a plurality of fluorides into the accelerator, so that the produced accelerator contains a large amount of fluoride ions, which causes serious harm to the production environment and constructors. In addition, the existing alkali-free liquid accelerator usually contains some insoluble substances to improve the performance of the accelerator, but the phenomenon of layering and precipitation can occur under the condition of long-term storage, and the stability of the accelerator is also adversely affected.
Disclosure of Invention
The invention aims to provide a chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator and a preparation method thereof, which can effectively improve the electrical insulation of sprayed concrete, enhance the chlorine ion permeation resistance of the sprayed concrete, improve the stability of a suspended liquid accelerator, meet the technical requirements of GB/T35159-2017 on alkali-free liquid accelerators under the condition of 7-8% of doping amount, and have the excellent characteristics of high early strength, high later strength retention rate, greenness, safety, environmental friendliness and the like. In addition, in the development process of the accelerator, the red mud is used as an experimental raw material to successfully prepare the high-concentration polyaluminium sulfate, so that the accelerating effect of the accelerator is ensured, the introduction of fluorine-containing components is avoided, and the resource utilization of the aluminum industrial waste is effectively realized. The invention can also solve the problem that the saline-alkali soil area has higher requirement on the chloride ion permeability resistance of the sprayed concrete, and overcomes the defect that the accelerator is used in the saline-alkali soil area.
The specific technical scheme of the invention is as follows:
the chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator comprises the following raw materials in parts by mass:
45-55 parts of high-concentration polyaluminum sulfate, 5-8 parts of a composite early strength agent, 2-3.5 parts of an insulating component, 1.5-2.5 parts of a composite rust inhibitor, 1-2 parts of a reinforcing agent, 0.3-0.6 part of a thickening agent, 0.25-0.75 part of an acidity regulator and 30-45 parts of deionized water.
Al in the high-concentration polyaluminium sulfate 2 O 3 The content can reach more than 25 wt%; compared with common industrial aluminum sulfate Al 2 O 3 Al in polyaluminium sulfate in an amount of 15 to 16 wt% 2 O 3 The content is remarkably improved, so thatThe polyaluminium sulfate can ionize more Al when dissolved in water 3+ And less SO 4 2- Under the same action and effect, the dosage of aluminum sulfate can be reduced, and the stability of the liquid accelerator can be improved.
The preparation method of the high-concentration polyaluminium sulfate comprises the following steps:
1) weighing the red mud, sequentially performing ball milling, drying and screening, and performing modification treatment at a high temperature of 900-1000 ℃ to improve the inherent activity of the red mud; adding a sulfuric acid solution into the modified red mud, stirring, and performing solid-liquid separation to obtain a solution A;
2) adjusting the pH value of the solution A within the range of 3-3.5, adding a potassium permanganate solution into the solution A, heating, stirring and reacting until the mass of a brown precipitate generated in the solution A is not increased any more, standing and cooling, and filtering to obtain a solution B;
3) dropwise adding calcium hydroxide emulsion into the solution B, heating and stirring to perform polymerization reaction, stopping dropwise adding the calcium hydroxide emulsion when the basicity reaches 30%, adding powdery pseudo-boehmite, continuously stirring, standing and cooling after the stirring is finished, fully filtering, and performing curing treatment on the solution to obtain the high-concentration polyaluminium sulfate.
The ball milling conditions in the step 1) are as follows: a planetary ball mill is adopted, the rotating speed of the ball mill is within the range of 250-300 r/min, and the ball milling time is within the range of 40-60 min;
the drying conditions in the step 1) are as follows: drying at 100-105 ℃, and drying the ground red mud to a constant weight state;
the screening conditions in the step 1) refer to that: the test sieve mesh number is 200 meshes, and the particle size of the sieved red mud powder is less than 75 microns;
the modification treatment time in the step 1) is within the range of 2-3 h;
dropwise adding a sulfuric acid solution in the step 1) according to a solid-liquid ratio of 7-10 mL/g; the volume fraction of the sulfuric acid solution is 40-50%;
the stirring in the step 1) is to fully stir for 45-60 min at the rotating speed of 300 r/min;
in the step 2), the pH value of the solution A is adjusted to be within the range of 3-3.5 by using dilute sulfuric acid;
in the step 2), the concentration of the potassium permanganate solution is in the range of 0.05-0.1 mol/L, and the volume ratio of the potassium permanganate solution to the solution A is 1: 12.5-15;
in the step 2), the heating and stirring reaction refers to: the heating temperature is within the range of 85-95 ℃, and the reaction time is within the range of 20-30 min; the stirring is carried out fully at the rotating speed of 300 r/min;
in the step 3), the preparation conditions of the calcium hydroxide emulsion are as follows: mixing calcium hydroxide and water, and stirring at a rotating speed of 250-300 r/min for 20-30 min to prepare a calcium hydroxide emulsion with a concentration of 10-20 wt%; preferably, the mass of the calcium hydroxide is within the range of 10-20 g, and the mass of the water is within the range of 80-90 g;
in the step 3), heating and stirring refer to controlling the water bath heating temperature to be within 70-80 ℃, and carrying out polymerization reaction at the rotating speed of 200r/min, wherein the reaction time is within 1.5-2 h;
in the step 3), the specific surface area of the powdery pseudo-boehmite is not less than 250m 2 The mass ratio of the solution B to the pseudo-boehmite is 10-10.5: 1;
adding the powdery pseudo-boehmite in the step 3), and continuously stirring for 20-30 min at the same rotating speed;
in the step 3), the curing treatment conditions are as follows: the curing time is within 10-12 h, and the curing temperature is within 65-80 ℃;
the composite early strength agent comprises the following components: is composed of triethanolamine and any one or two of diethanolamine, triisopropanolamine or diethanolisopropanolamine; the triethanolamine content is 18-25 wt%; in a cement hydration system, alcamines can complex Al 3+ 、Fe 3+ Plasma, the formed complex forms a large amount of soluble areas in the solution, the diffusion rate of hydration products is improved, and the early strength of the concrete is promoted to be increased. In the liquid accelerator system, the alcamines can react with Al 3+ Soluble complex ions are formed by complexation, and Al in the solution is reduced 3+ In a concentration of (2), enhanceStability of liquid accelerator. Meanwhile, the alcamines can increase the viscosity of the liquid accelerator and contribute to reducing the rebound rate of sprayed concrete.
The insulating component is any one of muscovite powder or sericite powder, and the particle size of the particles is distributed in the range of 1500-2000 meshes. The muscovite powder and the sericite powder have good electrical insulation, the resistivity of the sprayed concrete can be promoted to be remarkably improved, meanwhile, the muscovite powder or the sericite powder can be filled in the pore structure of the concrete in the construction process, on one hand, the compactness of the concrete is increased, on the other hand, the propagation path of chloride ions in the interior of the concrete is blocked to a great extent, and the chloride ion permeability resistance of the sprayed concrete is effectively enhanced.
The composite rust inhibitor is prepared by mixing amino alcohol, fatty acid ester and triethylene tetramine together, wherein the mass ratio of the amino alcohol to the fatty acid ester to the triethylene tetramine is 1 (1.5-2.5) to 1-2. The amino alcohol is selected from N-methyldiethanolamine or N, N-dimethylethanolamine, and the fatty acid ester is selected from glycerin fatty acid ester or propylene glycol fatty acid ester; the composite rust inhibitor has multiple rust inhibiting effects, fatty acid ester can generate hydrolysis reaction in an alkaline environment, formed acid radical negative ions can be combined with calcium ions in concrete, and generated fatty acid salt can form a layer of protective film in a cathode area in reinforced concrete, so that the corrosion of harmful substances such as chloride ions and the like on reinforcing steel bars is effectively avoided. The amino alcohol can also isolate harmful substances such as chloride ions in the cathode region in the reinforced concrete, so that the propagation path of the harmful substances such as chloride ions in the concrete is blocked. And the asymmetric electron pair of nitrogen atom that triethylene tetramine has can adsorb on the reinforcing bar surface, can effectively restrain the chemical reaction that the positive pole district takes place, further promotes reinforced concrete's anti erosion capacity.
The preparation method of the composite rust inhibitor comprises the following steps: sequentially adding amino alcohol, fatty acid ester and triethylene tetramine into a reaction kettle according to the formula amount, controlling the temperature of the reaction kettle within the range of 105-115 ℃, stirring for 150-180 min at the rotating speed of 300r/min, standing and cooling to obtain the composite rust inhibitor.
The reinforcing agent is any one of nano fumed silica or nano silica sol. The nano fumed silica has the performance characteristics of large specific surface area, strong reactivity and the like, meanwhile, silanol groups contained on the surface of the nano fumed silica can interact with adjacent silica particles to generate hydrogen bonds, and a thixotropic structure is formed by utilizing the action of the hydrogen bonds, so that insoluble substances can be uniformly dispersed in the accelerating agent and are not precipitated. The nano silica sol is a solution containing amorphous and uniformly dispersed nano silica particles, can also exert the performance advantage of strong reactivity of silica, can accelerate the hydration rate of cement minerals in the cement hydration process, shortens the setting time of cement slurry, and improves the compressive strength of concrete at each hydration age. Meanwhile, the nano-silicon dioxide also has a filling effect, so that the pore structure of the concrete can be effectively reduced, and the chloride ion permeability resistance of the concrete is further enhanced.
The thickening agent is any one of sodium bentonite, magnesium bentonite or calcium bentonite. The bentonite has good thickening property and thixotropy, can avoid the sedimentation of suspended particles in the accelerator, and enhances the stability of the accelerator. Meanwhile, the particle filling effect, the water absorption characteristic and the interaction between the bentonite and hydration products are beneficial to reducing the internal pore structure of the concrete, blocking the propagation path of chloride ions in the pore structure of the concrete and effectively enhancing the chloride ion permeability resistance of the concrete. Besides, the bentonite can also improve the cohesiveness of concrete mixture, and has good effect on reducing the rebound rate of sprayed concrete.
The acidity regulator is oxalic acid. Compared with other acids, the oxalic acid has a certain coagulation promoting effect and can shorten the setting time of the cement paste. Meanwhile, the oxalic acid can also reduce the pH value of the solution and inhibit Al 3+ The hydrolysis-polymerization-precipitation reaction of (2) is carried out, Al is increased 3+ Crystallization resistance, thereby improving the stability of the liquid accelerator system.
The invention provides a preparation method of a chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator, which comprises the following steps:
s1, mixing deionized water and a thickening agent according to the formula amount, stirring, sequentially adding a reinforcing agent and an insulating component, and continuously stirring to obtain a uniformly dispersed mixed solution;
s2, adding the mixed solution obtained in the step S1 into a reaction kettle filled with high-concentration polyaluminium sulfate according to the formula amount, heating and stirring, dropwise adding the compound early strength agent according to the formula amount into the reaction kettle, stirring for reaction, continuously dropwise adding the compound rust inhibitor into the reaction kettle, stirring, then adding oxalic acid, regulating and controlling the pH value of the solution to be 2.5-3.0, stirring, and naturally cooling to room temperature to obtain the chlorine ion permeation resistant fluorine-free alkali-free liquid accelerator.
In the step S1, the first stirring is carried out for 45-60 min at the rotating speed of 1800-2000 r/min;
in step S1, the continuous stirring is to continue stirring for 15-20 min at the same rotating speed,
in the step S2, the heating and stirring means that the temperature of the reaction kettle is controlled within a range of 65-75 ℃, and stirring is carried out for 25-30 min at a rotating speed of 300 r/min;
in step S2, the stirring reaction is to stop heating after stirring for 60min at the same temperature and rotation speed;
in the step S2, adding the composite rust inhibitor dropwise, stirring for 25-30 min, and then adding oxalic acid;
in the step S2, oxalic acid is added to regulate the pH value of the solution to be 2.5-3.0, and then the solution is stirred for 10-15 min;
compared with the prior art, the invention has the following advantages:
1. the chloride ion permeability resistance of the sprayed concrete is enhanced, the corrosion problem of chloride to the steel bars in saline-alkali land areas can be effectively solved, the service life of the steel bars in a sprayed layer is prolonged, the cost of reinforcing and maintaining the sprayed concrete is reduced, and the application of the alkali-free liquid accelerator in tunnel engineering is facilitated to popularize.
2. The stability of the suspension type liquid accelerator is improved, fine particles can be uniformly dispersed in the suspension, the sedimentation rate of the fine particles is obviously reduced, and Al is inhibited 3+ The hydrolysis reaction rate of the catalyst effectively delays the alkali-free reactionDestabilization time of the liquid accelerator.
3. The resource utilization of the aluminum industrial waste is realized, the high-concentration polyaluminium sulfate is prepared, the coagulation accelerating effect of the accelerator is ensured, the introduction of fluorine-containing components is avoided, and the harm of fluoride to the natural environment and the body health of construction personnel is effectively prevented. Meanwhile, the accelerator also has the characteristics of no alkali, no chlorine, no pungent smell and the like, has a good accelerating effect under the condition of low mixing amount, and is beneficial to improving the strength of cement mortar at different hydration ages.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
The invention is further described below, but the scope of protection of the invention is not limited to the following:
the preparation method of the calcium hydroxide emulsion used by the invention comprises the following steps: 15g of calcium hydroxide and 85g of water are mixed and stirred for 30min at the rotating speed of 300r/min to prepare 15 wt% calcium hydroxide emulsion.
The particle size of the used muscovite powder or sericite powder is distributed in the range of 1500-2000 meshes.
Example 1
The embodiment provides a chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator which is prepared from the following raw materials in parts by weight: 45 parts of self-made high-concentration polyaluminium sulfate, 5 parts of a composite early strength agent, 3.5 parts of muscovite powder, 2.5 parts of a composite rust inhibitor, 2 parts of nano fumed silica, 0.6 part of magnesium bentonite, 0.75 part of oxalic acid and 40.65 parts of deionized water; the compound early strength agent used: 18 wt% triethanolamine, 32 wt% diethanolamine and 50 wt% diethanol monoisopropanolamine.
The preparation method of the chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator comprises the following steps:
1) preparing high-concentration polyaluminium sulfate;
1-1) weighing 500g of red mud, and performing ball milling, drying, screening and other processes in sequence, wherein the ball milling parameters comprise: the rotating speed of the ball mill is 300r/min, the ball milling time is 40min, the ball-milled red mud is placed in a drying box at 105 ℃ to be dried to a constant weight state and is sieved by a 200-mesh test sieve, then modification treatment is carried out at the high temperature of 1000 ℃, and the specific time of the modification treatment is 2 h. Loading the modified red mud into a four-neck flask, dropwise adding a sulfuric acid solution with the prefabricated volume fraction of 40% according to the solid-liquid ratio of 7mL/g, fully stirring for 60min at the rotating speed of 300r/min, and obtaining a solution A by a solid-liquid separation technology;
1-2) adjusting the pH value of the solution A to be within the range of 3-3.5 by using dilute sulfuric acid, and adding 350g of a potassium permanganate solution with the concentration of 0.1mol/L into a four-neck flask filled with the solution A, wherein the volume ratio of the potassium permanganate solution to the solution A is 1: 15; controlling the heating temperature of the water bath to be about 95 ℃, simultaneously fully stirring at the rotating speed of 300r/min until the mass of the brown precipitate generated in the solution A is not increased any more, standing, cooling and filtering to obtain a solution B;
1-3) dropwise adding a prepared calcium hydroxide emulsion into a four-neck flask filled with the solution B, controlling the heating temperature of a water bath at 80 ℃, carrying out polymerization reaction at the rotating speed of 200r/min for 1.5h, stopping dropwise adding the calcium hydroxide emulsion when the basicity reaches 30%, and simultaneously carrying out the following steps according to the solution B: adding pseudo-boehmite into a four-neck flask according to the mass ratio of the pseudo-boehmite to 10.5:1, stirring for 30min at the same rotating speed, standing and coolingThen fully filtering, putting the solution into a curing tank for curing at 65 ℃ for 10h to obtain the Al 2 O 3 High-concentration polyaluminium sulfate with the content of 26 percent.
2) According to the set mass ratio, N-methyldiethanolamine: propylene glycol fatty acid ester: triethylene tetramine is 1: 2.5: 1.5 weighing corresponding raw materials, sequentially adding N-methyldiethanolamine, propylene glycol fatty acid ester and triethylene tetramine into a reaction kettle, controlling the temperature of the reaction kettle at 115 ℃, stirring for 180min at the rotating speed of 300r/min, standing and cooling to obtain the composite rust inhibitor.
3) According to the formula, a certain amount of deionized water is added into a four-neck flask, the weighed magnesium-based bentonite is added into the four-neck flask, the mixture is stirred at high speed for 60min at normal temperature, the rotating speed is controlled at 1800r/min, then the nano fumed silica and the superfine muscovite powder are sequentially added, and the mixture is stirred at the same rotating speed for 20min to obtain a uniformly dispersed mixed solution.
4) Adding the mixed solution obtained in the step 3) into a reaction kettle filled with self-made high-concentration polyaluminium sulfate with a formula amount, controlling the temperature of the reaction kettle within a range of 75 ℃, stirring at a rotating speed of 300r/min for 30min, dropwise adding the composite early strength agent into the reaction kettle, stirring at the same temperature and rotating speed for 60min, stopping heating, dropwise adding the prepared composite rust inhibitor into the reaction kettle, stirring for 30min, adding oxalic acid, regulating and controlling the pH value of the solution to be 2.5-3.0, stirring for 15min, and naturally cooling to a room temperature state to obtain the chlorine ion permeation resistant fluorine-free alkali-free liquid accelerator.
Example 2
The embodiment provides a chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator which is prepared from the following raw materials in parts by weight: 50 parts of self-made high-concentration polyaluminum sulfate, 6 parts of composite early strength agent, 3.5 parts of sericite powder, 1.5 parts of composite rust inhibitor, 2 parts of nano silica sol, 0.3 part of calcium bentonite, 0.5 part of oxalic acid and 36.2 parts of water; the composite early strength agent comprises the following components: 25 wt% triethanolamine and 75 wt% diethanolisopropanolamine.
The preparation method of the chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator comprises the following steps:
1) preparing high-concentration polyaluminium sulfate;
1-1) weighing 500g of red mud, and performing ball milling, drying, screening and other processes in sequence, wherein the ball milling parameters comprise: the rotating speed of the ball mill is 250r/min, the ball milling time is 60min, the ball-milled red mud is placed in a drying box at 105 ℃ to be dried to a constant weight state and is sieved by a 200-mesh test sieve, and then modification treatment is carried out at the high temperature of 900 ℃, wherein the specific time of the modification treatment is 3 h. Loading the modified red mud into a four-neck flask, dropwise adding a sulfuric acid solution with a prefabricated volume fraction of 50% according to a solid-liquid ratio of 9mL/g, fully stirring for 60min at a rotating speed of 300r/min, and obtaining a solution A by a solid-liquid separation technology;
1-2) adjusting the pH value of the solution A to be within the range of 3-3.5 by using dilute sulfuric acid, and adding 350g of a potassium permanganate solution with the concentration of 0.1mol/L into a four-neck flask filled with the solution A, wherein the volume ratio of the potassium permanganate solution to the solution A is 1: 14; controlling the heating temperature of the water bath to be about 95 ℃, simultaneously fully stirring at the rotating speed of 300r/min until the mass of the brown precipitate generated in the solution A is not increased any more, reacting for 25min, standing, cooling and filtering to obtain a solution B;
1-3) dropwise adding a prefabricated calcium hydroxide emulsion into a four-neck flask filled with the solution B, controlling the heating temperature of a water bath within 80 ℃, and carrying out polymerization reaction at the rotating speed of 200r/min for 2 h; stopping dropwise adding the calcium hydroxide emulsion when the basicity reaches 30%, and simultaneously, according to the solution B: adding pseudo-boehmite into a four-neck flask according to the mass ratio of the pseudo-boehmite to the pseudo-boehmite of 10:1, stirring for 30min at the same rotating speed, standing, cooling, fully filtering, placing the solution into a curing tank for curing at 70 ℃ for 12h to obtain the Al-containing material 2 O 3 High-concentration polyaluminium sulfate with the content of 28 percent.
2) According to the set mass ratio, N-methyldiethanolamine: glycerin fatty acid ester: triethylene tetramine is 1: 2: 2 weighing corresponding raw materials, sequentially adding N-methyldiethanolamine, glycerin fatty acid ester and triethylene tetramine into a reaction kettle, controlling the temperature of the reaction kettle at 115 ℃, stirring for 160min at the rotating speed of 300r/min, standing and cooling to obtain the composite rust inhibitor.
3) Adding quantitative deionized water into a four-neck flask, adding the weighed calcium-based bentonite into the four-neck flask, stirring at high speed for 60min at normal temperature, controlling the rotating speed at 1800r/min, sequentially adding nano silica sol and sericite powder, and stirring at the same rotating speed for 20min to obtain a uniformly dispersed mixed solution.
4) Adding the mixed solution obtained in the step 3) into a reaction kettle filled with self-made high-concentration polyaluminium sulfate, controlling the temperature of the reaction kettle at 75 ℃, stirring for 30min at the rotating speed of 300r/min, dropwise adding the composite early strength agent into the reaction kettle, stirring for 60min at the same temperature and rotating speed, stopping heating, dropwise adding the composite rust inhibitor into the reaction kettle, stirring for 30min, adding oxalic acid, regulating and controlling the pH value of the solution to be 2.5-3.0, stirring for 15min, and naturally cooling to the room temperature state to obtain the chlorine ion permeation resistant fluorine-free alkali-free liquid accelerator.
Example 3
The embodiment provides a chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator for sprayed concrete, which is prepared from the following raw materials in parts by weight: 55 parts of self-made high-concentration polyaluminum sulfate, 8 parts of composite early strength agent, 2 parts of muscovite powder, 1.5 parts of composite rust inhibitor, 1 part of nano fumed silica, 0.3 part of sodium bentonite, 0.25 part of oxalic acid and 31.95 parts of water; the composite early strength agent is as follows: 25 wt% triethanolamine, 25 wt% triisopropanolamine and 50 wt% diethanolisopropanolamine.
The preparation method of the chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator comprises the following steps:
1) preparing high-concentration polyaluminium sulfate;
1-1) weighing 500g of red mud, and performing ball milling, drying, screening and other processes in sequence, wherein the ball milling parameters comprise: the rotating speed of the ball mill is 300r/min, the ball milling time is 60min, the ball-milled red mud is placed in a drying box at 105 ℃ to be dried to a constant weight state and is sieved by a 200-mesh test sieve, then modification treatment is carried out at the high temperature of 1000 ℃, and the specific time of the modification treatment is 3 h. Loading the modified red mud into a four-neck flask, dropwise adding a sulfuric acid solution with a prefabricated volume fraction of 50% according to a solid-liquid ratio of 10mL/g, fully stirring for 60min at a rotating speed of 300r/min, and obtaining a solution A by a solid-liquid separation technology;
1-2) adjusting the pH value of the solution A to be within the range of 3-3.5 by using dilute sulfuric acid, and adding 350g of a 0.1mol/L potassium permanganate solution into a four-neck flask filled with the solution A, wherein the volume ratio of the potassium permanganate solution to the solution A is 1: 14.5; controlling the heating temperature of the water bath to be about 95 ℃, simultaneously fully stirring at the rotating speed of 300r/min until the mass of the brown precipitate generated in the solution A is not increased any more, standing, cooling and filtering to obtain a solution B;
1-3) dropwise adding a prepared calcium hydroxide emulsion into a four-neck flask filled with the solution B, controlling the heating temperature of a water bath at 80 ℃, carrying out polymerization reaction at the rotating speed of 200r/min for 2h, stopping dropwise adding the calcium hydroxide emulsion when the basicity reaches 30%, and simultaneously carrying out the following steps: adding pseudo-boehmite into a four-neck flask according to the mass ratio of the pseudo-boehmite to the pseudo-boehmite of 10:1, stirring for 30min at the same rotating speed, standing, cooling, fully filtering, placing the solution into a curing tank for curing at the temperature of 80 ℃ for 12h to obtain the Al-containing material 2 O 3 High-concentration polyaluminium sulfate with 29% content.
2) According to the set mass ratio, N, N-dimethylethanolamine: propylene glycol fatty acid ester: triethylene tetramine 1: 1.5: weighing corresponding raw materials, sequentially adding N, N-dimethylethanolamine, propylene glycol fatty acid ester and triethylene tetramine into a reaction kettle, controlling the temperature of the reaction kettle within the range of 115 ℃, stirring for 160min at the rotating speed of 300r/min, standing and cooling to obtain the composite rust inhibitor.
3) According to the formula amount, adding a certain amount of deionized water into a four-neck flask, adding the weighed sodium bentonite into the four-neck flask, stirring at a high speed for 60min at normal temperature, controlling the rotating speed at 1800r/min, sequentially adding the nano fumed silica and the muscovite powder, and stirring at the same rotating speed for 18min to obtain a uniformly dispersed mixed solution.
4) Adding the mixed solution obtained in the step 3) into a reaction kettle filled with self-made high-concentration polyaluminium sulfate, controlling the temperature of the reaction kettle within a range of 75 ℃, stirring for 30min at a rotating speed of 300r/min, dropwise adding a composite early strength agent into the reaction kettle, stirring for 60min at the same temperature and rotating speed, stopping heating, dropwise adding a composite rust inhibitor into the reaction kettle, stirring for 30min, adding oxalic acid, regulating and controlling the pH value of the solution to be 2.5-3.0, stirring for 15min, and naturally cooling to a room temperature state to obtain the chlorine ion permeation resistant fluorine-free alkali-free liquid accelerator.
Comparative example 1
The difference between the comparative example 1 and the example 1 is that the muscovite powder, the nano fumed silica and the composite rust inhibitor are not added in the comparative example 1, and the rest components and the content thereof are consistent with the example 1.
Namely, the fluoride-free alkali-free liquid accelerator provided in comparative example 1 is prepared from the following raw materials in parts by weight: 45 parts of self-prepared high-concentration polyaluminium sulfate, 5 parts of composite early strength agent (the specific formula is the same as that in example 1), 0.6 part of magnesium bentonite, 0.75 part of oxalic acid and 40.65 parts of water.
Comparative example 1a method for preparing a fluorine-free alkali-free liquid accelerator comprising the steps of:
1) preparation of high-concentration polyaluminium sulfate: the high-concentration polyaluminium sulfate used in comparative example 1 was prepared in the same manner as in example 1;
2) according to the formula, quantitative deionized water is added into a four-neck flask, the weighed magnesium-based bentonite is added into the four-neck flask, and the mixture is stirred at high speed for 60min at normal temperature, wherein the rotating speed is controlled at 1800r/min, so that a uniformly dispersed mixed solution is obtained.
3) Adding the mixed solution obtained in the step 2) into a reaction kettle filled with self-made high-concentration polyaluminium sulfate with a formula amount, controlling the temperature of the reaction kettle within a range of 75 ℃, stirring at a rotating speed of 300r/min for 30min, dropwise adding a composite early strength agent into the reaction kettle, stirring at the same temperature and rotating speed for 60min, stopping heating, adding oxalic acid, regulating and controlling the pH value of the solution to be 2.5-3.0, stirring for 15min, and then naturally cooling to a room temperature state to obtain the fluorine-free alkali-free liquid accelerator.
Comparative example 2
The difference between the comparative example 2 and the example 2 is that the sericite powder, the nano silica sol and the composite rust inhibitor are not added in the comparative example 2, and the rest components and the content thereof are consistent with those in the example 2.
The fluoride-free alkali-free liquid accelerator is prepared from the following raw materials in parts by weight: 50 parts of self-prepared high-concentration polyaluminium sulfate, 6 parts of a composite early strength agent (the specific formula is the same as that in example 2), 0.3 part of calcium bentonite, 0.5 part of oxalic acid and 36.2 parts of water.
The preparation method of comparative example 2 includes the following steps:
1) preparation of high-concentration polyaluminium sulfate: the high-concentration polyaluminium sulfate used in comparative example 2 was prepared in the same manner as in example 2;
2) according to the formula amount, adding quantitative deionized water into a four-neck flask, adding the weighed calcium bentonite into the four-neck flask, stirring at high speed for 60min at normal temperature, and controlling the rotating speed at 1800r/min to obtain a uniformly dispersed mixed solution.
3) Adding the mixed solution obtained in the step 2) into a reaction kettle filled with self-made high-concentration polyaluminium sulfate, controlling the temperature of the reaction kettle within a range of 75 ℃, stirring for 30min at a rotating speed of 300r/min, then dropwise adding a composite early strength agent into the reaction kettle, stirring for 60min at the same temperature and rotating speed, stopping heating, adding oxalic acid, regulating and controlling the pH value of the solution to be 2.5-3.0, stirring for 15min, and then naturally cooling to a room temperature state to obtain the fluorine-free alkali-free liquid accelerator.
Comparative example 3
The difference between the comparative example 3 and the example 3 is that the muscovite powder, the nano fumed silica and the composite rust inhibitor are not added in the comparative example 3, and the rest components and the content thereof are consistent with the example 3.
The fluoride-free alkali-free liquid accelerator is prepared from the following raw materials in parts by weight: 55 parts of self-prepared high-concentration polyaluminium sulfate, 8 parts of a composite early strength agent (the specific formula is the same as that in example 3), 0.3 part of sodium bentonite, 0.25 part of oxalic acid and 31.95 parts of water.
The preparation method comprises the following steps:
1) preparation of high-concentration polyaluminium sulfate: the high-concentration polyaluminium sulfate used in comparative example 3 was prepared in the same manner as in example 3;
2) adding quantitative deionized water into a four-neck flask, adding the weighed calcium bentonite into the four-neck flask, and stirring at high speed for 60min at normal temperature, wherein the rotating speed is controlled at 1800r/min, so as to obtain a uniformly dispersed mixed solution.
3) Adding the mixed solution obtained in the step 2) into a reaction kettle filled with self-made high-concentration polyaluminium sulfate, controlling the temperature of the reaction kettle within a range of 75 ℃, stirring for 30min at a rotating speed of 300r/min, then dropwise adding a composite early strength agent into the reaction kettle, stirring for 60min at the same temperature and rotating speed, stopping heating, adding oxalic acid, regulating and controlling the pH value of the solution to be 2.5-3.0, stirring for 15min, and then naturally cooling to a room temperature state to obtain the chlorine ion permeation resistant fluorine-free alkali-free liquid accelerator.
Comparative example 4
Comparative example 4 is different from example 1 only in that in comparative example 4, ordinary industrial polyaluminum sulfate is used instead of the homemade high-concentration polyaluminum sulfate, and the remaining components and their contents are identical to those of example 1.
Namely, the fluoride-free alkali-free liquid accelerator provided by the comparative example 4 is prepared from the following raw materials in parts by weight: 45 parts of common industrial polyaluminium sulfate, 5 parts of a composite early strength agent (the specific formula is the same as that in example 1), 3.5 parts of muscovite powder, 2.5 parts of a composite rust inhibitor, 2 parts of nano fumed silica, 0.6 part of magnesium bentonite, 0.75 part of oxalic acid and 40.65 parts of deionized water.
Comparative example 1a method for preparing a fluorine-free alkali-free liquid accelerator comprising the steps of:
1) according to the set mass ratio, N-methyldiethanolamine: propylene glycol fatty acid ester: triethylene tetramine 1: 2.5: 1.5 weighing corresponding raw materials, sequentially adding N-methyldiethanolamine, propylene glycol fatty acid ester and triethylene tetramine into a reaction kettle, controlling the temperature of the reaction kettle within the range of 115 ℃, stirring for 180min at the rotating speed of 300r/min, standing and cooling to obtain the composite rust inhibitor.
2) According to the formula, a certain amount of deionized water is added into a four-neck flask, the weighed magnesium-based bentonite is added into the four-neck flask, the mixture is stirred at high speed for 60min at normal temperature, the rotating speed is controlled at 1800r/min, then the nano fumed silica and the superfine muscovite powder are sequentially added, and the mixture is stirred at the same rotating speed for 20min to obtain a uniformly dispersed mixed solution.
3) Adding the mixed solution obtained in the step 2) into a reaction kettle filled with common industrial polyaluminium sulfate according to the formula amount, controlling the temperature of the reaction kettle within a range of 75 ℃, stirring at a rotating speed of 300r/min for 30min, dropwise adding a composite early strength agent into the reaction kettle, stirring at the same temperature and rotating speed for 60min, stopping heating, dropwise adding the prepared composite rust inhibitor into the reaction kettle, stirring for 30min, adding oxalic acid, regulating and controlling the pH value of the solution to be between 2.5 and 3.0, stirring for 15min, and then naturally cooling to the room temperature state to obtain the chloride ion permeation resistant fluorine-free alkali-free liquid accelerator.
When the chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator provided by the formulas and the preparation processes of the examples 1-3 and the comparative examples 1-4 is used, the dosage is 7-8% based on the weight of cement. The setting time of the cement paste and the compressive strength of cement mortar are correspondingly detected according to the requirements of Chinese national standard GB/T35159-2017 accelerator for sprayed concrete, and the stability of the accelerator is reasonably evaluated. In addition, the chlorine ion diffusion capacity of the concrete is measured according to the method specified in GB/T50082-2009 Standard for testing the long-term performance and the durability of the common concrete, so as to evaluate the chlorine ion permeation resistance of the concrete. The cement brand adopted in the following experiments is all conch cement with the model of PO 42.5.
The results of the performance tests of each example, comparative example and commercially available alkali-free liquid accelerator are shown in Table 1. The blank sample is a concrete sample without any accelerator.
Table 1 statistical results of the performance tests
As is apparent from Table 1, the fluoride-free and alkali-free liquid accelerator resistant to chloride ion permeation provided by the invention has good chloride ion permeation resistance, wherein the 28d electric flux of example 1 is only 780C. According to the performance test statistics results of the three groups of examples and the comparative example, the mica powder, the composite rust inhibitor and the nano fumed silica (or nano silica sol) play an important role in improving the concrete compactness and inhibiting the chloride ion permeability, and meanwhile, the compressive strength of the cement mortar test block at each hydration age can be effectively improved, and the accelerating effect and the stability of the accelerating agent are relatively small, so that the accelerating agent series can meet various technical requirements of GB/T35159-2017 on the alkali-free liquid accelerating agent under the condition of 7-8% of doping amount. As shown by the performance test statistics results of the example 1 and the comparative example 4, the self-prepared high-concentration polyaluminium sulfate remarkably improves the setting accelerating effect of the setting accelerator, and has no negative influence on the strength of cement mortar and the stability of the setting accelerator. According to the statistical results of the performance tests of the examples and the commercial alkali-free liquid accelerator, the two are relatively close to each other in the aspect of accelerating effect on the whole, but the commercial alkali-free liquid accelerator has obvious disadvantages in the aspect of resisting chloride ion permeability, and the examples also have certain advantages in the aspects of influence on the strength and stability of cement mortar.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The fluoride-free alkali-free liquid accelerator resistant to chloride ion permeation is characterized by comprising the following raw materials in parts by mass:
45-55 parts of high-concentration polyaluminum sulfate, 5-8 parts of composite early strength agent, 2-3.5 parts of insulating component, 1.5-2.5 parts of composite rust inhibitor, 1-2 parts of reinforcing agent, 0.3-0.6 part of thickening agent, 0.25-0.75 part of acidity regulator and 30-45 parts of deionized water.
2. The fluoride-free alkali-free liquid accelerator as claimed in claim 1, wherein Al in the high-concentration polyaluminium sulfate is contained in 2 O 3 The content can reach more than 25 percent.
3. The fluoride-free alkali-free liquid accelerator resistant to chloride ion permeation according to claim 1 or 2, wherein the high concentration polyaluminium sulfate is prepared by a method comprising:
1) weighing the red mud, sequentially performing ball milling, drying and screening, and simultaneously performing modification treatment at a high temperature of 900-1000 ℃; adding a sulfuric acid solution into the modified red mud, stirring, and carrying out solid-liquid separation to obtain a solution A;
2) adjusting the pH value of the solution A to be within the range of 3-3.5, adding a potassium permanganate solution into the solution A, heating, stirring and reacting until the mass of brown precipitates generated in the solution A is not increased any more, standing and cooling, and filtering to obtain a solution B;
3) dropwise adding calcium hydroxide emulsion into the solution B, heating and stirring to perform polymerization reaction, stopping dropwise adding the calcium hydroxide emulsion when the basicity reaches 30%, then adding pseudo-boehmite, continuously stirring, standing and cooling after the continuous stirring, fully filtering, and curing the solution to prepare the high-concentration polyaluminium sulfate.
4. The fluoride-free alkali-free liquid accelerator according to claim 1 or 2, wherein the composite early strength agent: is composed of triethanolamine and any one or two of diethanolamine, triisopropanolamine or diethanolisopropanolamine; the triethanolamine content is 18-25%.
5. The fluoride-free alkali-free liquid accelerator according to claim 1 or 2, wherein the insulating component is any one of muscovite powder or sericite powder.
6. The fluoride-free alkali-free liquid accelerator as claimed in claim 1, wherein the composite rust inhibitor is prepared by mixing amino alcohol, fatty acid ester and triethylene tetramine together, and the mass ratio of the three components is 1 (1.5-2.5) to 1-2.
7. The fluoride-free alkali-free liquid accelerator resistant to chloride ion permeation according to claim 1 or 6, wherein the preparation method of the composite corrosion inhibitor is as follows: sequentially adding amino alcohol, fatty acid ester and triethylene tetramine into a reaction kettle according to the formula ratio, controlling the temperature of the reaction kettle within the range of 105-115 ℃, stirring for 150-180 min at the rotating speed of 300r/min, standing and cooling to obtain the composite rust inhibitor; the amino alcohol is selected from N-methyldiethanolamine or N, N-dimethylethanolamine, and the fatty acid ester is selected from glycerin fatty acid ester or propylene glycol fatty acid ester.
8. The fluoride-free alkali-free liquid accelerator according to claim 1, wherein the reinforcing agent is any one of fumed silica or nanosilicon sol.
9. The fluoride-free alkali-free liquid accelerator according to claim 1, wherein the thickener is any one of sodium bentonite, magnesium bentonite and calcium bentonite.
10. A method for preparing a fluoride-free and alkali-free liquid accelerator resistant to chloride ion permeation according to any one of claims 1 to 9, comprising the steps of:
s1, mixing deionized water and a thickening agent according to the formula amount, stirring, then sequentially adding a reinforcing agent and an insulating component, and continuously stirring to obtain a uniformly dispersed mixed solution;
s2, adding the mixed solution obtained in the step S1 into a reaction kettle filled with high-concentration polyaluminium sulfate according to the formula amount, heating and stirring, dropwise adding the compound early strength agent according to the formula amount into the reaction kettle, stirring for reaction, continuously dropwise adding the compound rust inhibitor into the reaction kettle, stirring, then adding oxalic acid, regulating and controlling the pH value of the solution to be 2.5-3.0, stirring, and naturally cooling to room temperature to obtain the chlorine ion permeation resistant fluorine-free alkali-free liquid accelerator.
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