CN110627400B - Alkali-free accelerator and preparation method and application thereof - Google Patents
Alkali-free accelerator and preparation method and application thereof Download PDFInfo
- Publication number
- CN110627400B CN110627400B CN201911067059.1A CN201911067059A CN110627400B CN 110627400 B CN110627400 B CN 110627400B CN 201911067059 A CN201911067059 A CN 201911067059A CN 110627400 B CN110627400 B CN 110627400B
- Authority
- CN
- China
- Prior art keywords
- alkali
- parts
- stirring
- free accelerator
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to an alkali-free accelerator, a preparation method and application thereof, wherein the alkali-free accelerator comprises the following components in parts by weight: 30-65 parts of aluminum sulfate, 2-10 parts of organic amine, 3-10 parts of catalyst A, 1-3 parts of catalyst B, 3-6 parts of auxiliary agent and 25-50 parts of water; the catalyst A comprises a salt compound containing phosphoric acid groups and aluminum ions; the catalyst B comprises a compound containing carboxyl and hydroxyl. According to the invention, two different types of catalysts are introduced into an aluminum sulfate-organic amine reaction system, and the two catalysts have synergistic effect, so that the complex reaction of aluminum sulfate and organic amine is more complete, strong acids such as hydrofluoric acid are not required to be added, the alkali-free accelerator can be reduced, the rapid solidification rate is ensured, the one-day strength is higher, and the product is safe and reliable.
Description
Technical Field
The invention relates to the technical field of civil construction materials, in particular to an alkali-free accelerator and a preparation method and application thereof.
Background
At present, the alkali-free accelerator on the market is produced by reacting aluminum sulfate-organic amine as a base, and an aluminum ion complex is generated by the complex reaction of the aluminum sulfate and the organic amine, so that the effect of quickly reacting with cement to coagulate the cement is achieved; these are roughly divided into two types: firstly, a suspending agent or a dispersing agent is introduced on the basis of the reaction of aluminum sulfate and organic amine, so that the integral state of the alkali-free accelerator is maintained in a relatively stable suspension system on a physical level, the alkali-free accelerator has the performance required by construction, and meanwhile, certain storage performance can be ensured, and the defect that the alkali-free accelerator is extremely large in doping amount and cannot be stored for a long time in actual use is overcome; secondly, hydrofluoric acid or other strong acids are introduced on the basis of the reaction of aluminum sulfate and organic amine, so that the produced alkali-free accelerator has extremely strong condensation performance, and the defects are that the alkali-free accelerator has potential safety hazards and extremely low one-day strength. Therefore, a novel alkali-free accelerator which is safe, environment-friendly and stable in product is needed in the market to meet the requirements of various engineering constructions on the alkali-free accelerator.
CN104370489B alkali-free liquid accelerator is characterized by comprising the following components in percentage by mass: silicate salt: 3% -15%, aluminum sulfate: 35% -50%, organic amine: 5% -15%, stabilizer: 0% -3%, lithium salt: 0% -5%, the rest is water; the silicate is a magnesium silicate aqueous solution with a Baume degree of 31 and a modulus of 3.4. Compared with the product of the traditional process, the alkali-free liquid accelerator has the advantages of low rebound rate, short setting time, high early strength, small loss of later strength and almost no loss. The initial setting time is less than 5 minutes, the final setting time is less than 12 minutes, the one-day compressive strength is more than 6MPa, and the data show that the setting rate and the one-day strength of the accelerator still need to be further improved.
CN109761528A discloses an organic amine early strength type alkali-free accelerator for copper sulfate coagulation regulation and a preparation method thereof, wherein the raw materials are weighed according to the following mass percentage: 25-45% of hydrofluoric acid, 5-15% of aluminum hydroxide, 0.2-3% of organic amine, 14-40% of aluminum sulfate or polyaluminum sulfate, 15-35% of sodium sulfate, 5-10% of sodium hydroxide solution, 0.3-2% of copper sulfate, 0.1-0.5% of polyacrylamide and the balance of water, respectively grinding the aluminum sulfate or polyaluminum sulfate and the sodium sulfate into uniform fine powder, and sieving the fine powder with a 150-mesh sieve; sequentially adding the raw materials into a reaction kettle in sequence, controlling the temperature of reactants to be 50-90 ℃ during stirring, stirring for 30-50 minutes after the addition, and discharging to obtain the copper sulfate coagulation-regulating organic amine early-strength alkali-free accelerator. The copper sulfate coagulation-regulating organic amine early-strength alkali-free accelerator prepared by the invention does not contain alkali, the condensation time of sulfur trioxide in cement is effectively regulated by copper sulfate, the early strength is high, the later strength is high, the cost is moderate, the copper sulfate coagulation-regulating organic amine early-strength alkali-free accelerator can be widely applied to tunnel engineering and construction, and the preparation method is simple. However, the addition of a large amount of hydrofluoric acid in the formula brings certain potential safety hazards to construction, and simultaneously, the strength in one day is influenced.
CN100448791C discloses an alkali-free concrete accelerator and a processing method thereof, wherein the alkali-free concrete accelerator comprises, by weight, 30-65 parts of aluminum sulfate, 2-8 parts of organic amine, 1-5 parts of a suspending agent and 20-35 parts of water, the aluminum sulfate is ground and sieved by a sieve of 80-300 meshes, the aluminum sulfate is added into a mixed solution of the organic amine, the suspending agent and the water by weight, the mixed solution is dissolved at the temperature of 40-100 ℃, a high-speed stirrer is used for strongly stirring for 10-30 minutes, and the mixed solution is emulsified for 5-10 minutes by an emulsifying machine after being uniformly stirred, so that the required alkali-free liquid accelerator is obtained; grinding aluminum sulfate and organic amine, and sieving with 80-300 mesh sieve to obtain the alkali-free dry powder accelerator. The alkali-free accelerator disclosed by the invention is alkali-free, chlorine-free, free of pungent smell, good in cohesiveness, low in rebound quantity, high in later strength preservation rate and high in anti-permeability grade, and can bring a better working environment by adding the alkali-free accelerator into sprayed concrete. However, in the process of practical use, a large amount of alkali-free accelerator needs to be added to achieve a good setting effect, and the storage stability needs to be further improved.
Therefore, there is a need in the art to develop an alkali-free accelerator that can achieve rapid setting with a small doping amount, can be stored for a long period of time, is safe to use, and has high one-day strength.
Disclosure of Invention
The invention aims to provide an alkali-free accelerator which can realize quick solidification under the condition of small doping amount, is safe to use, can enable a base material to have higher one-day strength and has excellent later mechanical property of concrete.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an alkali-free accelerator which comprises the following components in parts by weight:
the catalyst A comprises a salt compound containing phosphoric acid groups and aluminum ions;
the catalyst B comprises a compound containing carboxyl and hydroxyl.
The content of aluminum sulfate in the alkali-free accelerator is 30-65 parts by weight, such as 31 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 64 parts by weight and the like;
the content of the organic amine in the alkali-free accelerator is 2 to 10 parts by weight, such as 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight and the like;
the content of the catalyst A in the alkali-free accelerator is 3 to 10 parts by weight, such as 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight and the like;
in the alkali-free accelerator, the content of the catalyst B is 1 to 3 parts by weight, such as 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight and the like;
in the alkali-free accelerator, the content of the auxiliary agent is 3-6 parts by weight, such as 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight and the like;
the alkali-free accelerator contains 25 to 50 parts by weight of water, for example, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 48 parts by weight, or the like.
According to the invention, two different types of catalysts are introduced into an aluminum sulfate-organic amine reaction system, and the two catalysts have synergistic effect, so that the complex reaction of aluminum sulfate and organic amine is more complete, strong acids such as hydrofluoric acid are not required to be added, the mixing amount of an alkali-free accelerator can be reduced, the rapid solidification rate is ensured, the one-day strength is higher, the mixing amount is 6% under the condition of reference cement, the 1-minute half initial setting and 5-minute 48-second final setting can be achieved, and the 1-day strength can reach 14 MPa. Meanwhile, the sprayed concrete added with the alkali-free accelerator has good later strength, the 28-day compressive strength ratio of the sprayed concrete can reach 110%, and the 90-day compressive strength retention rate is more than 100%.
In addition, no high-risk raw materials are introduced into the alkali-free accelerator, the pH value is controlled to be 3 +/-1, the product is safe and reliable, and the safe implementation of engineering construction can be guaranteed; no alkali ions were introduced, the alkali content was < 1%.
Preferably, the catalyst A comprises any one or at least two of aluminum dihydrogen phosphate, aluminum trihydrogen phosphate and aluminum phosphate.
Preferably, the catalyst B comprises any one or a combination of at least two of citric acid, lactic acid and glycolic acid.
Preferably, the aluminium sulphate comprises iron-free aluminium sulphate and/or iron-containing aluminium sulphate.
Preferably, the aluminum sulfate comprises aluminum sulfate octadecahydrate.
Preferably, the aluminum sulfate octadecahydrate comprises iron-containing aluminum sulfate octadecahydrate and/or iron-free aluminum sulfate octadecahydrate.
Preferably, the organic amine includes any one or a combination of at least two of diethanolamine, triethanolamine, ethanolamine, triisopropanolamine and diethanolisopropanolamine.
Preferably, the amine content of the organic amine is 80-100% (mass fraction), such as 81%, 82%, 85%, 87%, 89%, 90%, 92%, 94%, etc.
Preferably, the mass ratio of catalyst a to catalyst B is 2-8:1, such as 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, and the like.
The invention preferably selects the compounding ratio of the two catalysts to be 2-8:1, and under the ratio, the complex reaction of aluminum sulfate and organic amine can be further promoted, so that the coagulation effect of the alkali-free accelerator under low doping amount is improved.
Preferably, the auxiliary agent comprises any one or at least two combinations of a synergist, a stabilizer and a binder, and three combinations of the synergist, the stabilizer and the binder are preferred.
The invention preferably adds the synergist and the stabilizer at the same time, further enhances the coagulation effect of the alkali-free accelerator, can achieve no precipitation for 1 year in actual storage, and can not generate precipitation under low temperature conditions.
In addition, the binder component is added, so that the high temperature released by cement hydration can be utilized to promote the rapid polymerization reaction of substances under the alkaline condition, a large amount of high molecular substances are formed, the binding power of the concrete is increased, and the rebound quantity of the sprayed concrete is greatly reduced.
Preferably, the synergist is present in an amount of 0.5 to 10 parts by weight, such as 1 part by weight, 3 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 9 parts by weight, etc.
Preferably, the synergist comprises any one or at least two of L-ascorbic acid, fluosilicic acid, magnesium fluosilicate, ammonium fluoride and ammonium bifluoride.
Compared with hydrofluoric acid or other types of strong acids, the synergist is preferably used, so that the excellent condensation performance is guaranteed, the potential safety hazard is small, and the one-day strength cannot be influenced.
Preferably, the mass concentration of the fluosilicic acid is 30-50%, such as 35%, 40%, 45%, etc., preferably 40%.
Preferably, the stabilizer comprises any one or a combination of at least two of formic acid, phosphoric acid and acetic acid.
The weak acid is preferably selected as a stabilizer, so that the storage stability of the product is ensured, the potential safety hazard is reduced, and the higher one-day strength is ensured.
Preferably, the stabilizer is present in an amount of 2 to 4 parts by weight, such as 2.2 parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.7 parts by weight, 2.9 parts by weight, 3 parts by weight, 3.4 parts by weight, 3.8 parts by weight, and the like.
The binder comprises any one or at least two of acrylamide, acrylic acid, methacrylic acid, itaconic acid and AMPS.
Preferably, the binder is present in an amount of 0 to 10 parts by weight, such as 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, and the like;
preferably, the alkali-free accelerator comprises the following components in parts by weight:
the catalyst A comprises aluminum dihydrogen phosphate and/or aluminum trihydrogen phosphate;
the catalyst B comprises citric acid.
The second purpose of the invention is to provide a preparation method of the alkali-free accelerator, which comprises the following steps:
(1) mixing the aluminum sulfate, the organic amine, the catalyst A and water according to the formula ratio, and stirring to obtain an alkali-free accelerator stock solution;
(2) and mixing the catalyst B and the auxiliary agent with the alkali-free accelerator stock solution according to the formula ratio, and stirring to obtain the alkali-free accelerator.
Preferably, in step (1), the temperature of the mixing is 20 to 100 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and the like.
Preferably, step (1) specifically comprises: dissolving the aluminum sulfate, the organic amine and the catalyst A in the formula ratio in water;
preferably, in step (1), the stirring time is 60-120min, such as 80min, 90min, 100min, 110min, etc.
Preferably, in step (1), the stirring rate is 50-80rpm, such as 60rpm, 65rpm, 70rpm, 75rpm, and the like.
Preferably, the step (2) specifically comprises: adding the catalyst B in the formula amount into the alkali-free accelerator stock solution, stirring for the first time, adding the synergist in the formula amount, stirring for the second time, adding the stabilizer in the formula amount, stirring for the third time, adding the binder in the formula amount, and stirring for the fourth time to obtain the alkali-free accelerator.
Preferably, in the step (2), the time of the one-time stirring is 10-30min, such as 11min, 15min, 18min, 20min, 22min, 25min, 28min and the like.
Preferably, in the step (2), the time of the second stirring is 10-30min, such as 11min, 15min, 18min, 20min, 22min, 25min, 28min and the like.
Preferably, in the step (2), the time for stirring for three times is 10-20min, such as 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, and the like.
Preferably, in step (2), the four times of stirring are carried out for 10-30min, such as 11min, 15min, 18min, 20min, 22min, 25min, 28min and the like.
Preferably, the preparation method specifically comprises the following steps:
(1) dissolving aluminum sulfate, organic amine and catalyst A in a formula amount in water at 40-100 ℃, and stirring at the speed of 50-80rpm for 60-120min to obtain an alkali-free accelerator stock solution;
(2) adding the catalyst B in the formula amount into the alkali-free accelerator stock solution, stirring for 10-30min for the first time, adding the synergist in the formula amount, stirring for 10-30min for the second time, adding the stabilizer in the formula amount, stirring for 10-20min for the third time, adding the binder in the formula amount, and stirring for 10-30min for the fourth time to obtain the alkali-free accelerator.
The invention also provides cement which contains the alkali-free accelerator.
Preferably, the mass percentage of the alkali-free accelerator in the cement is 4-10%, such as 6%, 7%, 8%, 9%, etc., preferably 6-9%.
The fourth object of the present invention is to provide a concrete containing the cement of the third object.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, two different types of catalysts are introduced into an aluminum sulfate-organic amine reaction system, and the two catalysts have synergistic effect, so that the complex reaction of aluminum sulfate and organic amine is more complete, strong acids such as hydrofluoric acid are not required to be added, the mixing amount of an alkali-free accelerator can be reduced, the rapid solidification rate is ensured, the one-day strength is higher, the mixing amount is 6% under the condition of reference cement, the 1-minute half initial setting and 5-minute 48-second final setting can be achieved, and the 1-day strength can reach 14 MPa. Meanwhile, the sprayed concrete added with the alkali-free accelerator has good later strength, the 28d compressive strength ratio of the sprayed concrete can reach 110%, and the 90d compressive strength retention rate is more than 100%.
In addition, no high-risk raw materials are introduced into the alkali-free accelerator, the pH value is controlled to be 3 +/-1, the product is safe and reliable, and the safe implementation of engineering construction can be guaranteed; no alkali ions were introduced, the alkali content was < 1%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an alkali-free accelerator which comprises the following components in parts by weight:
the preparation method of the alkali-free accelerator comprises the following steps:
(1) dissolving the aluminum sulfate, the organic amine and the catalyst A in the formula ratio in water at the temperature of 80 ℃, and stirring at the speed of 70rpm for 100min to obtain an alkali-free accelerator stock solution;
(2) adding the catalyst B in the formula amount into the alkali-free accelerator stock solution, stirring for 20min, adding the synergist in the formula amount, stirring for 20min, adding the stabilizer in the formula amount, and stirring for 15min to obtain the alkali-free accelerator.
Example 2
The difference from example 1 is that 6 parts by weight of aluminum dihydrogen phosphate and 3 parts by weight of citric acid were used.
Example 3
The difference from example 1 is that 8 parts by weight of aluminum dihydrogen phosphate and 1 part by weight of citric acid were used.
Example 4
The difference from example 1 is that 5 parts by weight of aluminum dihydrogen phosphate and 4 parts by weight of citric acid were used.
Example 5
The difference from example 1 is that 8.5 parts by weight of aluminum dihydrogen phosphate and 0.5 part by weight of citric acid were used.
Example 6
The embodiment provides an alkali-free accelerator which comprises the following components in parts by weight:
the preparation method of the alkali-free accelerator comprises the following steps:
(1) dissolving the aluminum sulfate, the organic amine and the catalyst A in the formula ratio in water at 40 ℃, and stirring at the speed of 50rpm for 120min to obtain an alkali-free accelerator stock solution;
(2) adding the catalyst B in the formula amount into the alkali-free accelerator stock solution, stirring for 10min, adding the synergist in the formula amount, stirring for 10min, adding the stabilizer in the formula amount, and stirring for 10min to obtain the alkali-free accelerator.
Example 7
The embodiment provides an alkali-free accelerator which comprises the following components in parts by weight:
the preparation method of the alkali-free accelerator comprises the following steps:
(1) dissolving the aluminum sulfate, the organic amine and the catalyst A in the formula ratio in water at 100 ℃, and stirring at the speed of 80rpm for 60min to obtain an alkali-free accelerator stock solution;
(2) adding the catalyst B in the formula amount into the alkali-free accelerator stock solution, stirring for 30min, adding the synergist in the formula amount, stirring for 30min, adding the stabilizer in the formula amount, and stirring for 20min to obtain the alkali-free accelerator.
Example 8
The difference from example 1 is that no L-ascorbic acid (synergist) was added.
Example 9
The difference from example 1 is that no formic acid (stabilizer) is added.
Example 10
The difference from example 1 is that no L-ascorbic acid (synergist) and no formic acid (stabilizer) were added.
Example 11
The embodiment provides an alkali-free accelerator which comprises the following components in parts by weight:
the preparation method of the alkali-free accelerator comprises the following steps:
(1) dissolving the aluminum sulfate, the organic amine and the catalyst A in the formula ratio in water at the temperature of 80 ℃, and stirring at the speed of 80rpm for 100min to obtain an alkali-free accelerator stock solution;
(2) adding the catalyst B in the formula amount into the alkali-free accelerator stock solution, stirring for 20min, adding the synergist in the formula amount, stirring for 20min, adding the stabilizer in the formula amount, stirring for 15min, adding the binder in the formula amount, and stirring for 20min to obtain the alkali-free accelerator.
Example 12
The difference from example 11 is that acrylamide is replaced by an equal amount of acrylic acid.
Example 13
The difference from example 11 is that acrylamide is replaced by an equal amount of AMPS.
Comparative example 1
The difference from example 1 is that no aluminum dihydrogen phosphate is added and the citric acid is 10 parts by weight.
Comparative example 2
The difference from example 1 is that citric acid was not added and aluminum dihydrogen phosphate was 10 parts by weight.
And (3) performance testing:
(1) setting time and one-day strength test of cement doped with the alkali-free setting accelerators of examples and comparative examples, respectively: according to GB/T35159-2017 accelerator for sprayed concrete
Wherein, the mixing amount of the alkali-free accelerator in the cement is 6 percent;
(2) mechanical property test of concrete containing the alkali-free setting accelerators of examples and comparative examples, respectively:
JGJ55-2011 design rule of common concrete mix proportion, TB10424-2018 construction quality acceptance standard of railway concrete engineering, wherein the mix proportion of the sprayed concrete is as follows:
the polycarboxylic acid high-performance water reducing agent is K-PCA-R of Cleister, Guangzhou.
(3) Storage stability test of alkali-free setting accelerators of examples and comparative examples:
according to GB/T35159-2017 accelerator for sprayed concrete
The results of the performance tests are shown in tables 1 and 2.
TABLE 1 test data for cement
Table 2 test data for concrete
Where d represents day, \\ represents that the test was not performed, and stability refers to the volume of supernatant.
As can be seen from tables 1 and 2, the alkali-free accelerator provided by the invention has good setting effect under the condition of small mixing amount, the one-day strength of the cement is high, the initial setting time is 1min16 s to 8min 20s, the final setting time is 5min 48s to 15min 53s, the 1d strength is 6.2-14.5MPa, the 28d compressive strength ratio is 91-113%, and the 90d compressive strength retention rate is 101-108%, and when the alkali-free accelerator is used for concrete, the alkali-free accelerator can also have high mechanical property, the stability is 0-10mL, the 1d strength of the concrete is 21.3-26.9MPa, the 28d strength of the concrete is 44.5-55.3MPa, and the rebound rate is 0-15%.
The catalyst A is not added in the comparative example 1, the catalyst B is not added in the comparative example 2, the solidification effect of the finally obtained alkali-free accelerator is obviously deteriorated, and the one-day strength of the cement and the mechanical property of the concrete are reduced.
It is understood from comparative examples 1 to 5 that when the mass ratio of the catalyst A to the catalyst B is 2 to 8:1 (examples 1 to 3), the setting effect of the accelerator is the best, the strength of cement and concrete is the highest, and the overall performance is deteriorated when the amount of the catalyst A is too large or too small (examples 4 and 5).
Comparing example 1 with examples 11-13, the rebound rate of the concrete is obviously reduced after the binder is added (examples 11-13), because the binder can promote the rapid polymerization reaction of the substances by utilizing the high temperature released by cement hydration under the alkaline condition, so as to form a large amount of high molecular substances, increase the binding power of the concrete and greatly reduce the rebound amount of the sprayed concrete.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (23)
1. An alkali-free accelerator without hydrofluoric acid for preparing cement with initial setting time of 1min 20 s-2 min 10s, final setting time of 6min 12 s-7 min 10s, 1d strength of 8.9-14.5 MPa, 28d compressive strength ratio of 102-113% and 90d compressive strength retention rate of 101-108%, which is characterized by comprising the following components in parts by weight:
30-65 parts of aluminum sulfate
2-10 parts of organic amine
Catalyst A3-10 parts by weight
1-3 parts of catalyst B
0.5 to 10 portions of synergist
2-4 parts of stabilizer
0 to 10 parts by weight of binder
25-50 parts of water;
the catalyst A is aluminum dihydrogen phosphate;
the catalyst B is citric acid;
the mass ratio of the catalyst A to the catalyst B is 8: 1;
the synergist is any one or combination of at least two of L-ascorbic acid, fluosilicic acid, magnesium fluosilicate, ammonium fluoride and ammonium bifluoride;
the stabilizer is any one or combination of at least two of formic acid, phosphoric acid and acetic acid;
the binder is any one or at least two of acrylamide, acrylic acid, methacrylic acid, itaconic acid and AMPS.
2. The alkali-free accelerator according to claim 1, wherein the aluminum sulfate comprises non-iron aluminum sulfate and/or iron-containing aluminum sulfate.
3. The alkali-free accelerator of claim 1, wherein the aluminum sulfate comprises aluminum sulfate octadecahydrate.
4. The alkali-free accelerator according to claim 3, wherein the aluminum sulfate octadecahydrate comprises iron-containing aluminum sulfate octadecahydrate and/or iron-free aluminum sulfate octadecahydrate.
5. The alkali-free accelerator according to claim 1, wherein the organic amine comprises any one or a combination of at least two of diethanolamine, triethanolamine, ethanolamine, triisopropanolamine and diethanolisopropanolamine.
6. The alkali-free accelerator according to claim 1, wherein the organic amine has an amine content of 80 to 100% by mass.
7. The alkali-free accelerator according to claim 1, wherein the mass concentration of the fluorosilicic acid is 30 to 50%.
8. The alkali-free accelerator according to claim 1, wherein the mass concentration of the fluorosilicic acid is 40%.
9. A method for preparing an alkali-free accelerator according to any one of claims 1 to 8, comprising the steps of:
(1) mixing the aluminum sulfate, the organic amine, the catalyst A and water according to the formula ratio, and stirring to obtain an alkali-free accelerator stock solution;
(2) and mixing the catalyst B and the auxiliary agent with the alkali-free accelerator stock solution according to the formula ratio, and stirring to obtain the alkali-free accelerator.
10. The method according to claim 9, wherein the temperature of the mixing in the step (1) is 20 to 100 ℃.
11. The method according to claim 9, wherein the step (1) specifically comprises: the aluminum sulfate, the organic amine and the catalyst A with the formula amount are dissolved in water.
12. The method according to claim 9, wherein in the step (1), the stirring time is 60 to 120 min.
13. The production method according to claim 9, wherein in the step (1), the stirring rate is 50 to 80 rpm.
14. The method according to claim 9, wherein the step (2) specifically comprises: adding the catalyst B in the formula amount into the alkali-free accelerator stock solution, stirring for the first time, adding the synergist in the formula amount, stirring for the second time, adding the stabilizer in the formula amount, stirring for the third time, adding the binder in the formula amount, and stirring for the fourth time to obtain the alkali-free accelerator.
15. The method according to claim 14, wherein in the step (2), the time of the primary stirring is 10 to 30 min.
16. The method according to claim 14, wherein in the step (2), the time of the secondary stirring is 10 to 30 min.
17. The method according to claim 14, wherein in the step (2), the time for the third stirring is 10 to 20 min.
18. The method according to claim 14, wherein in the step (2), the four times of stirring is carried out for 10 to 30 min.
19. The method according to claim 14, wherein the method comprises the steps of:
(1) dissolving aluminum sulfate, organic amine and catalyst A in a formula amount in water at 40-100 ℃, and stirring at the speed of 50-80rpm for 60-120min to obtain an alkali-free accelerator stock solution;
(2) adding the catalyst B in the formula amount into the alkali-free accelerator stock solution, stirring for 10-30min for the first time, adding the synergist in the formula amount, stirring for 10-30min for the second time, adding the stabilizer in the formula amount, stirring for 10-20min for the third time, adding the binder in the formula amount, and stirring for 10-30min for the fourth time to obtain the alkali-free accelerator.
20. A cement characterized by containing the alkali-free accelerator as claimed in any one of claims 1 to 8.
21. The cement of claim 20, wherein the alkali-free setting accelerator is present in the cement in an amount of 4 to 10% by mass.
22. The cement of claim 20, wherein the alkali-free setting accelerator is present in the cement in an amount of 6 to 9% by mass.
23. A concrete comprising the cement of claim 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911067059.1A CN110627400B (en) | 2019-11-04 | 2019-11-04 | Alkali-free accelerator and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911067059.1A CN110627400B (en) | 2019-11-04 | 2019-11-04 | Alkali-free accelerator and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110627400A CN110627400A (en) | 2019-12-31 |
| CN110627400B true CN110627400B (en) | 2021-05-14 |
Family
ID=68978951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911067059.1A Active CN110627400B (en) | 2019-11-04 | 2019-11-04 | Alkali-free accelerator and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110627400B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111943560B (en) * | 2020-08-06 | 2022-09-09 | 武汉源锦建材科技有限公司 | Low-resilience alkali-free liquid accelerator and preparation method thereof |
| CN112408820B (en) * | 2020-11-27 | 2022-07-12 | 石家庄强力水泥厂 | Fly ash activity excitant, fly ash cement and preparation method thereof |
| CN113185182A (en) * | 2021-05-17 | 2021-07-30 | 传辰立新(厦门)科技有限公司 | High-strength durable alkali-free accelerator and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5976419B2 (en) * | 2012-06-26 | 2016-08-23 | デンカ株式会社 | Quick setting cement concrete and spraying method using the same |
| CN107473620A (en) * | 2017-08-11 | 2017-12-15 | 五家渠格辉新材料有限责任公司 | A kind of alkali-free liquid concrete accelerator and its preparation method and application |
| CN108483965A (en) * | 2018-05-18 | 2018-09-04 | 萧县沃德化工科技有限公司 | A kind of technique preparing accelerator using industrial waste phosphoric acid |
-
2019
- 2019-11-04 CN CN201911067059.1A patent/CN110627400B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110627400A (en) | 2019-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110627400B (en) | Alkali-free accelerator and preparation method and application thereof | |
| CN101648785B (en) | Alkali-free liquid setting accelerator | |
| CN105645823A (en) | Low-addition-amount environment-friendly alkali-free chlorine liquid accelerator and preparation method thereof | |
| CN105271867A (en) | Novel alkali-free liquid accelerator based on synthesis of polymeric aluminum sulfate | |
| CN111333362A (en) | Low-dosage high-early-strength alkali-free liquid accelerator and preparation method thereof | |
| CN110104984B (en) | Phosphogypsum slag cement early strength coagulant based on modified composite dehydration phase | |
| CN110028259B (en) | Neutral steel slag activated cementing material and preparation method and application thereof | |
| CN113135689A (en) | Elasticity-reducing low-sulfur alkali-free liquid accelerator and preparation method thereof | |
| CN112723787A (en) | Fluorine-free liquid accelerator and preparation method and application thereof | |
| CN113003976A (en) | Alkali-free liquid accelerator containing fluorosilicate and preparation method and application thereof | |
| CN108793806A (en) | A kind of alkali-free liquid accelerator and preparation method thereof | |
| CN110963732A (en) | Environment-friendly alkali-free liquid accelerator and normal-temperature preparation method thereof | |
| CN112028522B (en) | Low-alkali liquid accelerator and preparation method thereof | |
| CN111056762A (en) | Alkali-free liquid accelerator and preparation method thereof | |
| CN115636615A (en) | Alkali-free chlorine-free fluorine-free early strength type liquid accelerator and preparation method thereof | |
| CN113548825A (en) | Solid master batch of fluoride-free alkali-free liquid accelerator and preparation and use methods thereof | |
| CN113429149A (en) | High early strength alkali-free liquid accelerator and preparation method thereof | |
| CN115403294A (en) | High-stability alkali-free chlorine-free fluorine-free liquid accelerator and preparation method thereof | |
| CN114735961B (en) | Solid-liquid dual-purpose alkali-free accelerator and preparation method and application thereof | |
| CN110606696B (en) | Liquid alkali-free accelerator and normal-temperature synthesis process thereof | |
| CN111606598A (en) | Alkali-free accelerator and preparation process thereof | |
| CN107759126B (en) | Water reducing agent for sprayed concrete and preparation method thereof | |
| CN115353317B (en) | High-aluminum-content accelerator and preparation method thereof | |
| CN114702255B (en) | Super-sulfate cement prepared from low-activity acidic slag and preparation method thereof | |
| CN112520774A (en) | Preparation method of polyaluminum sulfate solution and alkali-free liquid accelerator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB03 | Change of inventor or designer information |
Inventor after: Lei Bin Inventor after: Fan Zhifeng Inventor after: Chen Tingguang Inventor after: Chen Liyong Inventor after: Wang Wenbo Inventor before: Lei Bin Inventor before: Liu Xuejun Inventor before: Yang Jie Inventor before: Yang Guang Inventor before: Chen Tingguang Inventor before: Luo Qiuping Inventor before: Chen Liyong Inventor before: Wang Wenbo Inventor before: Fan Zhifeng Inventor before: Cheng Jianqing Inventor before: Ye Junhong Inventor before: Jiao Zhiguo |
|
| CB03 | Change of inventor or designer information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A alkali free accelerator and its preparation method and application Effective date of registration: 20230915 Granted publication date: 20210514 Pledgee: Guangzhou Huadu Wansui Small Loan Co.,Ltd. Pledgor: GUANGZHOU KRYSTIC BUILDING MATERIALS Co.,Ltd. Registration number: Y2023980056691 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |