CN117430371A - Sulphoaluminate cement retarding enhancer and preparation process and application thereof - Google Patents
Sulphoaluminate cement retarding enhancer and preparation process and application thereof Download PDFInfo
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- CN117430371A CN117430371A CN202311379229.6A CN202311379229A CN117430371A CN 117430371 A CN117430371 A CN 117430371A CN 202311379229 A CN202311379229 A CN 202311379229A CN 117430371 A CN117430371 A CN 117430371A
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- 239000004568 cement Substances 0.000 title claims abstract description 99
- 239000003623 enhancer Substances 0.000 title claims abstract description 50
- 230000000979 retarding effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 91
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 48
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011975 tartaric acid Substances 0.000 claims abstract description 47
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 47
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 29
- 239000003381 stabilizer Substances 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 26
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 15
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 15
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920000858 Cyclodextrin Polymers 0.000 claims description 8
- 239000001116 FEMA 4028 Substances 0.000 claims description 8
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 8
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 8
- 229960004853 betadex Drugs 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- XTIIITNXEHRMQL-UHFFFAOYSA-N tripotassium methoxy(trioxido)silane Chemical compound [K+].[K+].[K+].CO[Si]([O-])([O-])[O-] XTIIITNXEHRMQL-UHFFFAOYSA-N 0.000 claims description 8
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 5
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical compound [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000003574 free electron Substances 0.000 claims 1
- 239000012744 reinforcing agent Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 229920001732 Lignosulfonate Polymers 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000003340 retarding agent Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910001653 ettringite Inorganic materials 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000008030 superplasticizer Substances 0.000 description 3
- -1 tartaric acid radical ions Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- GUPPESBEIQALOS-UHFFFAOYSA-L calcium tartrate Chemical compound [Ca+2].[O-]C(=O)C(O)C(O)C([O-])=O GUPPESBEIQALOS-UHFFFAOYSA-L 0.000 description 1
- 235000011035 calcium tartrate Nutrition 0.000 description 1
- 239000001427 calcium tartrate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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 the technical field of sulphoaluminate cement, in particular to a sulphoaluminate cement retarding enhancer, a preparation process and application thereof. The raw materials of the retarder enhancer comprise the following components: 15 to 28 parts of tartaric acid, 0.5 to 2 parts of nano silicon dioxide, 3 to 7 parts of polycarboxylate water reducer, 0.2 to 0.8 part of pH regulator, 1 to 6 parts of sodium gluconate, 0.1 to 0.5 part of dispersing agent, 0.5 to 3 parts of ferric nitrate, 0.3 to 0.8 part of stabilizer and 60 to 78 parts of water. The retarder reinforcing agent prepared by the invention not only can keep good retarder effect under high temperature condition, but also can make the interior of cement more compact and improve mechanical strength.
Description
Technical Field
The invention relates to the technical field of sulphoaluminate cement, in particular to a sulphoaluminate cement retarding enhancer, a preparation process and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The sulphoaluminate cement is green low-carbon cement and has the advantages of early strength, freezing resistance, impermeability, low alkalinity, sulfate erosion resistance and the like. Because of its fast setting time and high early strength, it is used in various first-aid repair engineering. However, the setting time is fast, namely a double-edged sword, the initial setting of the sulphoaluminate cement can be achieved in about 5 minutes, ettringite precipitation can be formed rapidly after the sulphoaluminate cement contacts with water, and a large amount of heat can be released in a short time due to the excessively fast hydration speed, so that the matrix temperature is excessively high, and further heat cracking is generated. The rapid setting of the sulphoaluminate cement causes the sulphoaluminate cement to lose fluidity in a short time, can meet construction requirements for general engineering, but cannot be applied to large-volume engineering. The high temperature environment in summer can further accelerate the hydration of the sulphoaluminate cement, shorten the setting time and further limit the application of the sulphoaluminate cement. Setting time is therefore an important reason for restricting the application of sulphoaluminate cement construction.
Setting time of the sulphoaluminate cement is prolonged by adding retarders such as citric acid, boric acid and the like into the sulphoaluminate cement, so that the construction workability of the sulphoaluminate cement is maintained for a certain period of time. Although the retarder has good effect in improving the setting time of the sulphoaluminate cement under the normal temperature condition (about 20 ℃), the use of the retarder is limited due to the problems, and the main reasons of the retarder include: (1) The high amount of retarder incorporated reduces the strength of the sulphoaluminate cement material. (2) At high temperature (30-50 ℃) in summer, the retarding effect of the retarder can be greatly reduced along with the rising of the temperature, and even the retarding effect is lost.
Disclosure of Invention
Aiming at the problems, the invention provides the sulphoaluminate cement retarder enhancer, the preparation process and the application thereof, and the retarder enhancer not only can maintain a good retarder effect under a high-temperature condition, but also can enable the interior of cement to be more compact and improve the mechanical strength. In order to achieve the above purpose, the present invention discloses the following technical solutions.
Firstly, the invention provides a sulphoaluminate cement retarder enhancer, which comprises the following raw materials in parts by weight: 15 to 28 parts of tartaric acid, 0.5 to 2 parts of nano silicon dioxide, 3 to 7 parts of polycarboxylate water reducer, 0.2 to 0.8 part of pH regulator, 1 to 6 parts of sodium gluconate, 0.1 to 0.5 part of dispersing agent, 0.5 to 3 parts of ferric nitrate, 0.3 to 0.8 part of stabilizer and 60 to 78 parts of water.
Further, the pH adjuster includes: potassium methyl silicate, sodium methyl silicate, and the like. In the present invention, the pH value of the pH regulator system is used to make the Fe provided by the ferric nitrate 3+ Better coordinates with tartaric acid.
Further, the dispersant includes: alpha-cyclodextrin, beta-cyclodextrin, etc. In the invention, the dispersing agent is utilized to help promote the dispersibility of the nano silicon dioxide.
Further, the stabilizer comprises: ethylene glycol, polyethylene glycol, and the like. In the invention, the stabilizer and tartaric acid are used for crosslinking and esterification reaction, so that the molecular weight of tartaric acid is increased, the carbon chain structure is increased, a more stable structure is formed, and the high temperature resistance of the obtained retarder enhancer is improved.
Further, the water reducing rate of the polycarboxylate water reducer is 25-30%.
Secondly, the invention provides a preparation process of a sulphoaluminate cement retarding enhancer, which comprises the following steps:
(1) And adding the ferric nitrate into water to form a solution A for standby.
(2) And adding the tartaric acid and the stabilizer into the rest water to form a solution B for later use.
(3) And heating the solution B, uniformly dripping the solution A into the heated solution B, and simultaneously adding the pH regulator to regulate the pH of the reaction system to be acidic. And (3) continuing stirring under the heating condition after the completion of the process to obtain a solution C, and then adding the polycarboxylate superplasticizer and the sodium gluconate, and mixing until the mixture is dissolved to obtain a solution D.
(4) And mixing the nano silicon dioxide, the dispersing agent and the solution D, and then performing ultrasonic dispersion to obtain the retarding enhancer.
Further, in the step (1), the weight ratio of the ferric nitrate to the water is 0.5-3: 5 to 20.
Further, in the step (3), the solution B is heated to 55 to 80 ℃.
Further, in the step (3), the pH of the reaction system is adjusted to be between 4.8 and 5.5 so that Fe provided by the ferric nitrate 3+ Better coordinates with tartaric acid.
Further, in the step (3), the stirring is continued for 2.5 to 3 hours. In this process, the stabilizer is mixed with tartaric acid and Fe 3+ The complex is formed by bridging coordination, so that the retarder prepared by the method has good stability in sulphoaluminate cement even under the high-temperature environment.
Further, in the step (4), the ultrasonic dispersion time is 15-20 min. The agglomerated nano-silica is uniformly dispersed in water by ultrasonic waves in the process.
Finally, the invention provides application of the retarder reinforcing agent obtained by the preparation process in sulphoaluminate cement. Optionally, the mass ratio of the retarder enhancer added into the sulphoaluminate cement is 2-8%.
The invention takes tartaric acid as a matrix and utilizes a stabilizer and Fe 3+ The retarder reinforcing agent with high temperature resistance and good dispersibility is prepared by coordination, and the setting time of the sulphoaluminate cement is effectively prolonged. This is due to: dissociation of-OH in tartaric acid followed by Fe 3+ The tartaric acid and the stabilizer are combined to generate crosslinking and esterification reaction, so that the molecular weight of the tartaric acid is increased, the carbon chain structure is increased, a more stable structure is formed, and the high temperature resistance of the tartaric acid is improved, so that the retarder enhancer disclosed by the invention stably exists in cement even under the high temperature condition. Meanwhile, the retarder enhancer of the invention utilizes hydroxyl groups in tartaric acidAnd carboxyl group can chelate Ca 2+ The calcium tartrate forming characteristic is combined, when the retarding enhancer of the invention is added into the sulphoaluminate cement, ca in the sulphoaluminate cement can be reduced 2+ The concentration of the cement can inhibit supersaturation conditions required by ettringite nucleation and growth, and prolong the setting time of the cement. Simultaneously, tartaric acid is adsorbed on the surface of the cement particles to prevent the tartaric acid from contacting with water, so that the dissolution rate of minerals in the cement particles is reduced, and the setting time of cement is further prolonged. With the increase of time, tartaric acid is gradually neutralized and consumed by alkaline cement hydration product calcium hydroxide, so that the retarding effect of tartaric acid is gradually weakened, cement particles are more fully contacted with water, and as ions adsorbed on the surfaces of the cement particles have negative charges (the negative charges of the tartaric acid radical ions are caused by-COO-in the tartaric acid), electrostatic repulsion is generated by the same charges among the cement particles, the cement particles are more uniformly dispersed, more free water exists among the cement particles, and the cement hydration is more fully carried out. In addition, the high activity of the nano silicon dioxide enables the nano silicon dioxide to react with calcium hydroxide which is a hydration product of cement to generate C-S-H gel, and the nano silicon dioxide has good filling effect on needle-shaped ettringite; and the nano silicon dioxide can play a role of nano filler, can well fill micro-nano pores, and improves the pore structure of cement, so that the cement is more compact, and the strength of the cement is improved.
Compared with the traditional retarder tartaric acid (the molecular structural formula is shown as the following formula 1), the sulphoaluminate cement retarder enhancer (the molecular structural formula is shown as the following formula 2) has obvious difference, and the upper part of the retarder enhancer is a polymer generated by condensation reaction between ethylene glycol and tartaric acid. The dashed line represents coordination bond, fe 3+ With empty electron orbitals, while the lone electron pair of carboxyl groups in tartaric acid on carboxylate ions formed in water is combined with Fe 3+ The empty electron orbitals form coordination bonds, and simultaneously tartaric acid molecules which do not undergo condensation reaction with ethylene glycol also react with Fe through lone electrons on carboxylate ions 3+ Coordination connection.
Compared with the prior art, the technical scheme of the invention has at least the following beneficial effects:
aiming at the problem of too high setting speed of sulphoaluminate cement, the traditional method generally adopts retarders such as boric acid, citric acid and the like, which can be adsorbed on the surfaces of cement particles to form semi-permeable or impermeable layers to prevent the cement particles from contacting with water, thereby delaying the hydration of cement. Over time the impermeable layer will gradually disappear and the cement particles will begin to hydrate upon contact with water. However, the high temperature has an inhibition effect on the dispersion of retarders such as boric acid, citric acid and the like, and the high temperature resistance of the boric acid and the citric acid is poor, and a complete impermeable layer cannot be formed on the surface of cement particles under the high temperature condition, so that the retarding effect of the retarder is not exerted, and the cement strength is negatively influenced. Therefore, the novel sulphoaluminate cement retarder reinforcing agent provided by the invention not only has a good high-temperature retarder effect, but also can induce ettringite to form in a nano in-situ induction mode, so that the strength of the sulphoaluminate cement is effectively improved. Through tests, the setting retarder can prolong the setting time of the sulphoaluminate cement from 10-20 min to more than 60min of the traditional retarder at a high temperature (30-50 ℃), and effectively solves the problem that the sulphoaluminate cement is difficult to construct at a high temperature in summer. In addition, compared with the traditional retarder, the retarder reinforcing agent provided by the invention has the advantages that the porosity of the sulphoaluminate cement is lower, and the strength of the sulphoaluminate cement is effectively improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a sample view of the retarder enhancer prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The reagents or materials used in the present invention may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications.
In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The technical scheme of the invention is further described with reference to the specification, the drawings and the specific embodiments.
Example 1
A preparation process of a sulphoaluminate cement retarding enhancer comprises the following steps:
(1) The following raw materials are taken: 20 parts of tartaric acid, 1.5 parts of solid gas-phase nano silicon dioxide, 3 parts of dispersing agent (beta-cyclodextrin 0.35 parts), 3 parts of sodium gluconate, 0.45 part of pH regulator (potassium methyl silicate), 5 parts of polycarboxylate water reducer (water reducing rate 30%), 2 parts of ferric nitrate, 0.5 part of stabilizer (ethylene glycol) and 70 parts of water.
(2) The ferric nitrate is added to 10 parts by weight of water to form a solution A for use.
(3) The tartaric acid and stabilizer were added to the remaining 60 parts by weight of water to form solution B for use.
(4) And heating the solution B to 60 ℃ in a water bath, uniformly dropwise adding the solution A into the solution B, and simultaneously adding the pH regulator to regulate the pH of a reaction system to 5.2. And (3) continuously stirring for 2 hours under the heating condition after the completion of the stirring to obtain a solution C, and then adding the polycarboxylate water reducer and the lignosulfonate, and magnetically stirring until the polycarboxylate water reducer and the lignosulfonate are completely dissolved to obtain a solution D.
(5) And mixing the nano silicon dioxide, the dispersing agent and the solution D, and performing ultrasonic dispersion for 20 minutes to obtain the retarding enhancer, as shown in figure 1.
1. The experimental samples were previously left at constant temperature of 40℃for one day. The sulfoaluminate cement, water and the retarder enhancer prepared in this example were mixed in an amount of 500g:143g:2g of the mixture was mixed to form a cement slurry, and the setting time was measured at 40℃according to GB/T1346-2011, the results of which are shown in the following table.
2. Sulphoaluminate cement, standard sand and water are mixed according to the ratio of 1:3: mixing the materials according to the mass ratio of 0.5, then doping the retarder reinforcing agent prepared in the embodiment, which is 2% of the mass of the sulphoaluminate cement, uniformly stirring, and pouring the mixture into a mould to prepare a test block. The test block was then tested for compressive strength according to GB/T17671-2021 and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Example 1 | 66 | 78 | 58.2 |
Example 2
A preparation process of a sulphoaluminate cement retarding enhancer comprises the following steps:
(1) The following raw materials are taken: 28 parts of tartaric acid, 2 parts of solid gas-phase nano silicon dioxide, 6 parts of dispersing agent (beta-cyclodextrin 0.5 parts), 6 parts of sodium gluconate, 0.8 part of pH regulator (potassium methyl silicate), 7 parts of polycarboxylate water reducer (water reducing rate 25%), 3 parts of ferric nitrate, 0.8 part of stabilizer (ethylene glycol) and 78 parts of water.
(2) The ferric nitrate is added to 20 parts by weight of water to form a solution A for later use.
(3) The tartaric acid and stabilizer were added to the remaining 58 parts by weight of water to form solution B for use.
(4) And heating the solution B to 60 ℃ in a water bath, uniformly dropwise adding the solution A into the solution B, and simultaneously adding the pH regulator to regulate the pH of a reaction system to 5.5. And (3) continuously stirring for 2 hours under the heating condition after the completion of the stirring to obtain a solution C, and then adding the polycarboxylate water reducer and the lignosulfonate, and magnetically stirring until the polycarboxylate water reducer and the lignosulfonate are completely dissolved to obtain a solution D.
(5) And mixing the nano silicon dioxide, the dispersing agent and the solution D, and performing ultrasonic dispersion for 15min to obtain the retarding and reinforcing agent.
The cement paste containing the retarder enhancer prepared in this example was tested for the test setting time and the compressive strength of the test block in the same manner as in example 1 above, and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Example 2 | 62 | 73 | 54.6 |
Example 3
A preparation process of a sulphoaluminate cement retarding enhancer comprises the following steps:
(1) The following raw materials are taken: 15 parts of tartaric acid, 0.5 part of solid gas-phase nano silicon dioxide, 0.1 part of dispersing agent (alpha-cyclodextrin), 1 part of sodium gluconate, 0.2 part of pH regulator (sodium methyl silicate), 3 parts of polycarboxylate water reducer (water reducing rate 25%), 0.5 part of ferric nitrate, 0.3 part of stabilizer (polyethylene glycol) and 60 parts of water.
(2) The ferric nitrate was added to 5 parts by weight of water to form solution a for use.
(3) The tartaric acid and stabilizer were added to the remaining 55 parts by weight of water to form solution B for use.
(4) And heating the solution B to 60 ℃ in a water bath, uniformly dropwise adding the solution A into the solution B, and simultaneously adding the pH regulator to regulate the pH of a reaction system to 4.8. And (3) continuously stirring for 2 hours under the heating condition after the completion of the stirring to obtain a solution C, and then adding the polycarboxylate water reducer and the lignosulfonate, and magnetically stirring until the polycarboxylate water reducer and the lignosulfonate are completely dissolved to obtain a solution D.
(5) And mixing the nano silicon dioxide, the dispersing agent and the solution D, and performing ultrasonic dispersion for 15min to obtain the retarding and reinforcing agent.
The cement paste containing the retarder enhancer prepared in this example was tested for the test setting time and the compressive strength of the test block in the same manner as in example 1 above, and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Example 3 | 60 | 75 | 55.7 |
Example 4
A preparation process of a sulphoaluminate cement retarding enhancer comprises the following steps:
(1) The following raw materials are taken: 20 parts of tartaric acid, 1.5 parts of solid gas-phase nano silicon dioxide, 3 parts of dispersing agent (beta-cyclodextrin 0.35 parts), 3 parts of sodium gluconate, 0.45 part of pH regulator (potassium methyl silicate), 5 parts of polycarboxylate water reducer (water reducing rate 30%), 0.5 part of stabilizer (ethylene glycol) and 70 parts of water.
(2) And adding the tartaric acid and the stabilizer into the water to form a solution B for later use.
(3) After heating the solution B to 60 ℃ in a water bath, adding the pH regulator into the solution B to regulate the pH of the reaction system to 5.2. And (3) continuously stirring for 2 hours under the heating condition after the completion of the stirring to obtain a solution C, and then adding the polycarboxylate water reducer and the lignosulfonate, and magnetically stirring until the polycarboxylate water reducer and the lignosulfonate are completely dissolved to obtain a solution D.
(4) And mixing the nano silicon dioxide, the dispersing agent and the solution D, and performing ultrasonic dispersion for 20min to obtain the retarding and reinforcing agent.
The cement paste containing the retarder enhancer prepared in this example was tested for the test setting time and the compressive strength of the test block in the same manner as in example 1 above, and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Example 4 | 27 | 32 | 49.5 |
Example 5
A preparation process of a sulphoaluminate cement retarding enhancer comprises the following steps:
(1) The following raw materials are taken: 20 parts of tartaric acid, 1.5 parts of solid gas-phase nano silicon dioxide, 3 parts of dispersing agent (beta-cyclodextrin 0.35 parts), 3 parts of sodium gluconate, 0.45 part of pH regulator (potassium methyl silicate), 5 parts of polycarboxylate water reducer (water reducing rate 30%), 2 parts of ferric nitrate and 70 parts of water.
(2) The ferric nitrate is added to 10 parts by weight of water to form a solution A for use.
(3) The tartaric acid was added to the remaining 60 parts by weight of water to form solution B for use.
(4) And heating the solution B to 60 ℃ in a water bath, uniformly dropwise adding the solution A into the solution B, and simultaneously adding the pH regulator to regulate the pH of a reaction system to 5.2. And (3) continuously stirring for 2 hours under the heating condition after the completion of the stirring to obtain a solution C, and then adding the polycarboxylate water reducer and the lignosulfonate, and magnetically stirring until the polycarboxylate water reducer and the lignosulfonate are completely dissolved to obtain a solution D.
(5) And mixing the nano silicon dioxide, the dispersing agent and the solution D, and performing ultrasonic dispersion for 20min to obtain the retarding and reinforcing agent.
The cement paste containing the retarder enhancer prepared in this example was tested for the test setting time and the compressive strength of the test block in the same manner as in example 1 above, and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Example 5 | 30 | 36 | 51.7 |
Example 6
A preparation process of a sulphoaluminate cement retarding enhancer comprises the following steps:
(1) The following raw materials are taken: 28 parts of tartaric acid, 0.5 part of dispersing agent (beta-cyclodextrin), 6 parts of sodium gluconate, 0.8 part of pH regulator (potassium methyl silicate), 7 parts of polycarboxylate water reducer (water reducing rate 25%), 3 parts of ferric nitrate, 0.8 part of stabilizer (ethylene glycol) and 78 parts of water.
(2) The ferric nitrate is added to 20 parts by weight of water to form a solution A for later use.
(3) The tartaric acid and stabilizer were added to the remaining 58 parts by weight of water to form solution B for use.
(4) And heating the solution B to 60 ℃ in a water bath, uniformly dropwise adding the solution A into the solution B, and simultaneously adding the pH regulator to regulate the pH of a reaction system to 5.5. And (3) continuously stirring for 2 hours under the heating condition after the completion of the stirring to obtain a solution C, and then adding the polycarboxylate water reducer and the lignosulfonate, and magnetically stirring until the polycarboxylate water reducer and the lignosulfonate are completely dissolved to obtain a solution D.
(5) And mixing the dispersing agent with the solution D, and performing ultrasonic dispersion for 15min to obtain the retarding and reinforcing agent.
The cement paste containing the retarder enhancer prepared in this example was tested for the test setting time and the compressive strength of the test block in the same manner as in example 1 above, and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Example 6 | 65 | 74 | 48.2 |
Example 7
A preparation process of a sulphoaluminate cement retarding enhancer comprises the following steps:
(1) The following raw materials are taken: 15 parts of tartaric acid, 0.5 part of solid gas-phase nano silicon dioxide, 0.2 part of pH regulator (sodium methyl silicate), 6 parts of dispersing agent (alpha-cyclodextrin 0.1 part), 0.5 part of sodium carbonate, 0.3 part of stabilizer (polyethylene glycol) and 60 parts of water.
(2) The ferric nitrate was added to 5 parts by weight of water to form solution a for use.
(3) The tartaric acid and stabilizer were added to the remaining 55 parts by weight of water to form solution B for use.
(4) And heating the solution B to 60 ℃ in a water bath, uniformly dropwise adding the solution A into the solution B, and simultaneously adding the pH regulator to regulate the pH of a reaction system to 4.8. And (3) continuing stirring for 2 hours under the heating condition after the completion of the stirring, so as to obtain a solution C, and then adding the sodium gluconate, and magnetically stirring until the sodium gluconate is completely dissolved, so as to obtain a solution D.
(5) And mixing the nano silicon dioxide, the dispersing agent and the solution D, and performing ultrasonic dispersion for 15min to obtain the retarding and reinforcing agent.
The cement paste containing the retarder enhancer prepared in this example was tested for the test setting time and the compressive strength of the test block in the same manner as in example 1 above, and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Example 7 | 56 | 63 | 51.9 |
Example 8
A preparation process of a sulphoaluminate cement retarding enhancer comprises the following steps:
(1) The following raw materials are taken: 28 parts of tartaric acid, 2 parts of solid gas-phase nano silicon dioxide, 0.8 part of dispersing agent (beta-cyclodextrin 0.5 part), 0.8 part of pH regulator (potassium methyl silicate), 7 parts of polycarboxylate water reducer (water reducing rate 25%), 3 parts of ferric nitrate, 0.8 part of stabilizer (ethylene glycol) and 78 parts of water.
(2) The ferric nitrate is added to 20 parts by weight of water to form a solution A for later use.
(3) The tartaric acid and stabilizer were added to the remaining 58 parts by weight of water to form solution B for use.
(4) And heating the solution B to 60 ℃ in a water bath, uniformly dropwise adding the solution A into the solution B, and simultaneously adding the pH regulator to regulate the pH of a reaction system to 5.5. And (3) continuing stirring for 2 hours under the heating condition after the completion of the stirring to obtain a solution C, and then adding the polycarboxylate superplasticizer, and magnetically stirring until the polycarboxylate superplasticizer is completely dissolved to obtain a solution D.
(5) And mixing the nano silicon dioxide, the dispersing agent and the solution D, and performing ultrasonic dispersion for 15min to obtain the retarding and reinforcing agent.
The cement paste containing the retarder enhancer prepared in this example was tested for the test setting time and the compressive strength of the test block in the same manner as in example 1 above, and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Example 8 | 57 | 65 | 54.3 |
Example 9
A preparation process of a sulphoaluminate cement retarding enhancer comprises the following steps:
(1) The following raw materials are taken: 15 parts of tartaric acid, 0.5 part of solid gas-phase nano silicon dioxide, 1 part of dispersing agent (alpha-cyclodextrin 0.1 part), 3 parts of sodium gluconate, 3 parts of polycarboxylate water reducer (water reducing rate 25%), 0.5 part of ferric nitrate, 0.3 part of stabilizer (polyethylene glycol) and 60 parts of water.
(2) The ferric nitrate was added to 5 parts by weight of water to form solution a for use.
(3) The tartaric acid and stabilizer were added to the remaining 55 parts by weight of water to form solution B for use.
(4) And heating the solution B to 60 ℃ in a water bath, uniformly dropwise adding the solution A into the solution B, continuously stirring the solution B for 2 hours under the heating condition to obtain a solution C, and adding the polycarboxylate water reducer and sodium gluconate, and magnetically stirring the solution C until the solution D is completely dissolved to obtain the solution D.
(5) And mixing the nano silicon dioxide, the dispersing agent and the solution D, and performing ultrasonic dispersion for 15min to obtain the retarding and reinforcing agent.
The cement paste containing the retarder enhancer prepared in this example was tested for the test setting time and the compressive strength of the test block in the same manner as in example 1 above, and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Example 9 | 48 | 55 | 50.4 |
Example 10
1. The experimental samples were previously left at constant temperature of 40℃for one day. Boric acid, citric acid and tartaric acid serving as traditional retarders are respectively mixed with sulphoaluminate cement and water according to 2g:500g:143g: is mixed to form a cement slurry and then tested for setting time according to GB/T1346-2011 at 40℃with the results shown in the following table.
2. Sulphoaluminate cement, standard sand and water are mixed according to the ratio of 1:3: mixing the materials according to the mass ratio of 0.5, respectively doping the traditional retarder boric acid, citric acid and tartaric acid with the mass of 0.4 percent of that of the sulphoaluminate cement, uniformly stirring, and pouring the mixture into a mould to prepare a test block. The test block was then tested for compressive strength according to GB/T17671-2021 and the results are shown in the following table.
| Performance index | Initial setting time/min | Final setting time/min | 28d compressive Strength/MPa |
| Boric acid | 14 | 18 | 40.2 |
| Citric acid | 16 | 20 | 42.6 |
| Tartaric acid | 12 | 16 | 44.5 |
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The cement retarder enhancer is characterized by having the following structural formula:
wherein the dotted line represents the lone pair of electrons on the carboxyl group in tartaric acid and Fe 3+ Coordination bonds formed by the free electron orbitals of the (C).
2. The sulphoaluminate cement retarder enhancer is characterized by comprising the following raw materials: 15 to 28 parts of tartaric acid, 0.5 to 2 parts of nano silicon dioxide, 3 to 7 parts of polycarboxylate water reducer, 0.2 to 0.8 part of pH regulator, 1 to 6 parts of sodium gluconate, 0.1 to 0.5 part of dispersing agent, 0.5 to 3 parts of ferric nitrate, 0.3 to 0.8 part of stabilizer and 60 to 78 parts of water.
3. The sulfoaluminate cement retarder enhancer of claim 1, wherein the pH adjustor comprises: potassium methyl silicate, sodium methyl silicate.
4. The sulfoaluminate cement retarder enhancer of claim 1, wherein the dispersant comprises: alpha-cyclodextrin and beta-cyclodextrin.
5. The sulfoaluminate cement retarder enhancer of any one of claims 1-4, wherein the stabilizer comprises: any one of ethylene glycol and polyethylene glycol.
6. The process for preparing the sulphoaluminate cement retarder enhancer of any one of claims 1 to 5, which is characterized by comprising the following steps:
adding the ferric nitrate into water to form a solution A for standby;
adding the tartaric acid and a stabilizer into the rest of the water to form a solution B for later use;
heating the solution B, uniformly dripping the solution A into the heated solution B, and simultaneously adding the pH regulator to regulate the pH of a reaction system to be acidic; continuously stirring under the heating condition after the completion to obtain a solution C, and then adding the polycarboxylate water reducer and sodium gluconate, and mixing until the mixture is dissolved to obtain a solution D;
and mixing the nano silicon dioxide, the dispersing agent and the solution D, and then performing ultrasonic dispersion to obtain the retarding enhancer.
7. The process for preparing the sulphoaluminate cement retarder enhancer of claim 6, wherein the weight ratio of the ferric nitrate to the water is 0.5-3: 5 to 20.
8. The process for preparing a sulphoaluminate cement retarder enhancer according to claim 5, wherein the solution B is heated to 55-80 ℃; optionally, the pH of the reaction system is adjusted to between 4.8 and 5.5.
9. The process for preparing a sulphoaluminate cement retarder enhancer according to any one of claims 6 to 8, wherein the time for continuing to stir is 2.5 to 3 hours;
optionally, the ultrasonic dispersion time is 15-20 min.
10. Use of a cement retarder enhancer according to claim 1 or a retarder enhancer obtainable by a process according to any one of claims 6 to 9 in a sulphoaluminate cement; optionally, the mass ratio of the retarder enhancer added into the sulphoaluminate cement is 2-8%.
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