CN115321868A - Application of cryolite in preparation of accelerator - Google Patents
Application of cryolite in preparation of accelerator Download PDFInfo
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- CN115321868A CN115321868A CN202211119810.XA CN202211119810A CN115321868A CN 115321868 A CN115321868 A CN 115321868A CN 202211119810 A CN202211119810 A CN 202211119810A CN 115321868 A CN115321868 A CN 115321868A
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- acid
- cryolite
- percent
- accelerator
- liquid accelerator
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- 229910001610 cryolite Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 33
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 30
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims abstract description 24
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 24
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 alcohol amine Chemical class 0.000 claims abstract description 12
- 239000004567 concrete Substances 0.000 claims abstract description 12
- 239000011378 shotcrete Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 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 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- IOXPXHVBWFDRGS-UHFFFAOYSA-N hept-6-enal Chemical compound C=CCCCCC=O IOXPXHVBWFDRGS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000009966 trimming Methods 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/12—Acids or salts thereof containing halogen in the anion
- C04B22/126—Fluorine compounds, e.g. silico-fluorine compounds
-
- 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)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical field of building materials, and particularly relates to an application of cryolite in preparation of an accelerator. According to the invention, the cryolite is added into the accelerator, and the synthesis conditions are regulated to prepare the liquid accelerator for sprayed concrete. The liquid accelerator is prepared by mixing the following raw materials in parts by mass: 0 to 7 percent of aluminum fluoride, 40 to 80 percent of aluminum sulfate, 1.2 to 8 percent of cryolite, 1 to 5 percent of hydroxycarboxylic acid, 4 to 10 percent of organic alcohol amine, 1 to 5 percent of inorganic acid and the balance of water. The liquid accelerator prepared by the invention has good stability, high setting speed and small rebound quantity, can effectively reduce the waste of concrete, and has higher practical value in the application of sprayed concrete.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to an application of cryolite in preparation of an accelerator.
Background
In the prior art, the accelerating agent can be divided into a powder accelerating agent and a liquid accelerating agent according to different preparation modes of concrete. The powder accelerator is mainly used for dry-process sprayed concrete, but the dry spraying has the defects of large dust, uneven doping, high resilience and the like; the liquid accelerator is mainly used for wet-process sprayed concrete, and wet spraying gradually replaces a dry spraying process due to the advantages of good construction environment, low resilience rate, high construction quality and the like, and particularly, a wet spraying process is more commonly adopted for excavation and support construction of large-scale hydro-junction engineering. The accelerator is used based on the principle that aluminum sulfate (the main accelerating component in the accelerator) and the components in the cement react chemically, so that the setting speed of the concrete is increased.
Aluminum sulfate as a component of the accelerator has a good accelerating effect, but the solubility of aluminum sulfate is not high enough, and when saturated solution of aluminum sulfate is used as the liquid accelerator, the requirement of qualified accelerator products can be met when the doping amount reaches 12%. Therefore, it is necessary to improve the concrete setting effect of the aluminum sulfate system accelerator at a lower dosage by improving the solubility of aluminum sulfate and the like.
The Chinese patent with the publication number of CN105271877B discloses a liquid accelerator and a preparation method thereof, wherein the accelerator is prepared by mixing 5-15% of aluminum sulfate, 5-15% of alcohol amine, solubilizer and accelerator, and is used for spraying concrete, the mixing amount of the liquid accelerator is generally 5-8% of the mass of cement, the accelerating effect is good, and the stability is high. But the parameters such as the solidification performance, the compressive strength and the like are still not high, and the higher performance requirements cannot be met.
Sodium hexafluoroaluminate (cryolite) is a common electrolytic fluxing agent, is commonly used as a fluxing agent for alumina electrolysis and pure aluminum refining, and has the characteristics of good stability, high melting point, difficult decomposition and volatilization and good conductivity; can also be used as artificial stone, multi-bell coating, trimming agent of steel and the like; in addition, the cryolite can also be used as an abrasion-resistant filler of a resin grinding wheel, a light-screening agent of glass, an opalescent agent of enamel, an insecticide of pesticide and the like. Because the natural cryolite has very little storage amount, the cryolite is mainly prepared by manual work.
Based on the method, the F in the cryolite is utilized by adding the cryolite component into the accelerating agent - Super strong complex Al 3+ Thereby increasing Al in the solution 3+ Or the concentration of free aluminum increases the stability of aluminum sulfate, and can achieve good coagulation promoting effect under the condition of low doping amount of aluminum fluoride complex ions.
Disclosure of Invention
The invention aims to provide an application of cryolite in preparing an accelerator, wherein the cryolite is added into the accelerator, and the synthesis conditions are regulated to prepare the liquid accelerator for sprayed concrete.
In order to achieve the purpose, the invention adopts the following technical scheme:
an application of cryolite in preparing a sprayed concrete liquid accelerator.
Furthermore, the invention utilizes cryolite to prepare a sprayed concrete liquid accelerator, which is prepared by aluminum fluoride, aluminum sulfate, cryolite, hydroxycarboxylic acid, organic (alcohol) amine (or polyalcohol), inorganic acid and the like through complex reaction; the liquid accelerator is prepared by mixing the following raw materials in percentage by mass: 0 to 7 percent of aluminum fluoride, 40 to 80 percent of aluminum sulfate, 1.2 to 8 percent of cryolite (the specific addition amount of the cryolite is 3 to 10 percent of the aluminum sulfate), 1 to 5 percent of hydroxycarboxylic acid, 4 to 10 percent of organic alcohol amine, 1 to 5 percent of inorganic acid and the balance of water.
Based on a general inventive concept, the present invention also provides a preparation method of the liquid accelerator, comprising the steps of:
(1) Mixing water, aluminum sulfate and cryolite, heating to 50-100 ℃, and stirring (stirring time is 60-150 minutes) until the solution is clear;
(2) And (2) adding an aluminum fluoride solution into the clear solution obtained in the step (1), uniformly mixing at the temperature of 50-80 ℃ (the mixing time is 60-150 minutes), then adding hydroxycarboxylic acid, after completely dissolving (the dissolving time is 30-60 minutes), sequentially adding organic alcohol amine and inorganic acid aqueous solution, and cooling to room temperature to obtain the liquid accelerator product.
Specifically, the aluminum sulfate in step (1) is industrial-grade aluminum sulfate, and is more preferably aluminum sulfate octadecahydrate.
Specifically, the cryolite in the step (1) is one or a mixture of more than two of single cryolite, calcined cryolite and silicon cryolite, and preferably the silicon cryolite.
Specifically, the amount of cryolite added in step (1) is more preferably 5% to 7% of aluminum sulfate.
Specifically, the temperature of the aluminum sulfate and the cryolite in the step (1) for reaction in water is preferably 50-95 ℃, and the stirring time is preferably 80-120 minutes; further, the temperature of the aluminum sulfate and cryolite reacted in the water in the step (1) is preferably 50 to 70 ℃.
Specifically, the aluminum fluoride solution is prepared by the following steps:
adding aluminum hydroxide into fluosilicic acid or hydrofluoric acid at the temperature of 80-100 ℃, stirring and dissolving for 30-80 minutes, and filtering to obtain a clear solution to prepare an aluminum fluoride solution.
Specifically, the concentration of the fluosilicic acid or the hydrofluoric acid is 15wt% -40 wt%.
More preferably, the preparation temperature of the aluminum fluoride solution is 90-100 ℃, and the stirring time is 30-60 minutes.
Specifically, in the step (2), the hydroxycarboxylic acid is one or a mixture of two or more of citric acid, salicylic acid, tartaric acid and lactic acid, and preferably lactic acid.
Further preferably, the amount of the hydroxycarboxylic acid added in the step (2) is 1 to 3wt% of the clear solution in the step (1).
Specifically, the organic alcohol amine in the step (2) is monoethanolamine, diethanolamine or triethanolamine, preferably diethanolamine or triethanolamine.
Further preferably, the addition amount of the organic alcohol amine in the step (2) is 4-7 wt% of the clear solution in the step (1).
Specifically, the inorganic acid in the step (2) is one or a mixture of more than two of hydrofluoric acid, phosphoric acid, nitric acid and sulfuric acid; the concentration of the inorganic acid aqueous solution is 5wt% -15 wt%.
Based on one general inventive concept, the invention also provides application of the liquid accelerator in improving the setting performance of concrete.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides an application method of chemical product cryolite (especially silicon cryolite) in the field of building, which utilizes F-superstrong complex Al in cryolite 3+ Thereby increasing Al in the solution 3+ Or the concentration of free aluminum, so that the stability of the aluminum sulfate is improved; on the other hand, the reaction activity ratio of the fluorine-aluminum complex ion is Al 3+ Higher, and achieves good coagulation promoting effect under lower fluorine-aluminum complex ion doping amount.
2. The liquid accelerator prepared by the invention is prepared from the raw materials of aluminum sulfate, inorganic acid and the like containing sulfate radicals, phosphate radicals, nitric acid and the like, so that the requirements on impurities in cryolite such as fluorine, aluminum, sodium, silicon dioxide, ferric oxide, calcium oxide, sulfate radicals, phosphate radicals and the like are low; in the preparation of the aluminum fluoride solution, a low-grade phosphate fertilizer byproduct, namely fluosilicic acid, and low-grade hydrofluoric acid, such as hydrofluoric acid etching solution and the like, can be used.
3. The liquid accelerator prepared by the invention has good stability, high setting speed and small rebound quantity, can effectively reduce the waste of concrete, and has higher practical value in the application of sprayed concrete.
Detailed Description
The technical solutions of the present application are described below clearly and completely with reference to the following embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and 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 application.
The experimental procedures without specifying specific conditions in the following examples were carried out under the usual conditions or conditions recommended by the manufacturers, and the starting materials and reagents used were all conventional commercial products without specific description.
The aluminum sulfate in the following examples is aluminum sulfate octadecahydrate; the cryolite is silicon cryolite; the hydroxycarboxylic acid is lactic acid.
The mass fractions and specifications of the components of cryolite used in the present invention are shown in table 1 below.
TABLE 1
Example 1
A preparation method of a liquid accelerator comprises the following specific steps;
(1) Respectively adding 280.6g of water, 500g of aluminum sulfate and 30g of cryolite into a reactor I, heating to 60 ℃, stirring for 90 minutes for full dissolution and complete complex reaction, wherein the solution is clear;
(2) Adding 71.5g of hydrofluoric acid with the concentration of 30wt% into a reactor II, adding 27.9g of aluminum hydroxide at the temperature of 95 ℃, stirring for 45 minutes, filtering to obtain a clear solution, and reacting to prepare an aluminum fluoride solution;
(3) And (3) cooling the aluminum fluoride solution obtained in the step (2) to about 60 ℃, adding the aluminum fluoride solution into a reactor I, uniformly mixing at the temperature of 60 ℃ (the mixing time is 60 minutes), adding 20g of hydroxycarboxylic acid, after the hydroxycarboxylic acid is completely dissolved (the dissolving time is 35 minutes), sequentially adding 50g of diethanolamine and 20g of inorganic acid aqueous solution (in the embodiment, 5wt% of phosphoric acid is adopted), and cooling to room temperature to obtain a liquid accelerator product.
Example 2
A preparation method of a liquid accelerator comprises the following specific steps;
(1) Respectively adding 271.4g of water, 520g of aluminum sulfate and 30g of cryolite into a reactor I, heating to 70 ℃, stirring for 100 minutes for full dissolution and complete complex reaction, wherein the solution is clear;
(2) Adding 57.1g of fluosilicic acid with the concentration of 30wt% into a reactor II, adding 18.6g of aluminum hydroxide at the temperature of 95 ℃, stirring for 30 minutes, filtering to obtain a clear solution, and reacting to prepare an aluminum fluoride solution;
(3) And (3) cooling the aluminum fluoride solution obtained in the step (2) to about 70 ℃, adding the aluminum fluoride solution into a reactor I, uniformly mixing at the temperature of 70 ℃ (the mixing time is 80 minutes), naturally cooling to 60 ℃, adding 20g of hydroxycarboxylic acid, after complete dissolution (the dissolution time is 45 minutes), sequentially adding 70g of diethanolamine and 20g of inorganic acid aqueous solution (7 wt% sulfuric acid is adopted in the embodiment), and cooling to room temperature to obtain a liquid accelerator product.
Example 3
A preparation method of a liquid accelerator comprises the following specific steps;
(1) Adding 254.0g of water, 600g of aluminum sulfate and 36g of cryolite into a reactor I respectively, heating to 50 ℃, stirring for 120 minutes for full dissolution and complete complex reaction, wherein the solution is clear;
(2) And (2) adding 30g of hydroxycarboxylic acid into the clear solution obtained in the step (1), after the hydroxycarboxylic acid is completely dissolved (the dissolving time is 30 minutes), sequentially adding 70g of diethanolamine and 20g of inorganic acid aqueous solution (specifically, 7wt% of nitric acid), and cooling to room temperature to obtain a liquid accelerator product.
Comparative example 1
Comparative example 1 provides a common preparation method of a liquid accelerator of an aluminum sulfate/aluminum fluoride system in the prior art, an aluminum fluoride solution is prepared first, and then the accelerator is prepared by compounding the aluminum fluoride solution with aluminum sulfate, alcohol amine, a stabilizer and the like, and the specific steps are as follows:
(1) Adding 71.5g of hydrofluoric acid with the concentration of 30wt% into a reactor, heating to 95 ℃, adding 27.9g of aluminum hydroxide, stirring for 45 minutes, filtering to obtain a clear solution, and reacting to prepare an aluminum fluoride solution;
(2) Cooling the aluminum fluoride solution obtained in the step (1) to about 60 ℃, respectively adding 310.6g of water and 500g of aluminum sulfate into a reactor, stirring for 90 minutes until the water and the aluminum sulfate are fully dissolved and the complexing reaction is complete to obtain a composite solution, wherein the composite solution is clear;
(3) And (3) adding 20g of hydroxycarboxylic acid into the composite solution obtained in the step (2), stirring for 45 minutes until the hydroxycarboxylic acid is completely dissolved, sequentially adding 50g of diethanolamine and 20g of inorganic acid aqueous solution (specifically 5wt% phosphoric acid), and cooling to room temperature to obtain a liquid accelerator product.
Referring to accelerating agent for shotcrete (GB/T35159-2017), the liquid accelerating agent products prepared in examples 1-3 of the present invention and comparative example 1 were added to concrete prepared from a reference cement, standard sand and water, respectively, and the performance of the accelerating agent was tested, and the results of the related tests are shown in Table 2. (blank set in Table 2 is a concrete test block prepared from only the reference cement, standard sand and water)
TABLE 2 setting time and compressive strength Properties of the liquid accelerator products prepared in the examples
| Detection group | The mixing amount of the accelerator is% | Initial setting time/s | Final setting time/s | 1 day compressive strength/Mpa | 28 days compressive Strength ratio% |
| Blank space | --- | --- | --- | --- | 100 |
| Example 1 | 5 | 221 | 401 | 8.3 | 94.8 |
| Example 2 | 3 | 204 | 394 | 9.1 | 91.9 |
| Example 3 | 3 | 218 | 417 | 7.9 | 93.4 |
| Comparative example 1 | 7 | 243 | 577 | 7.5 | 90.2 |
As can be seen from Table 2, the liquid setting accelerators prepared in the embodiments 1 to 3 of the invention meet the requirements of initial setting time, final setting time, early strength and later strength, can effectively improve the setting performance of concrete, and effectively improve the early strength and the later strength of the concrete.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Application of cryolite in preparing a sprayed concrete liquid accelerator.
2. The sprayed concrete liquid accelerator prepared from cryolite is characterized by being prepared by mixing the following raw materials in percentage by mass: 0 to 7 percent of aluminum fluoride, 40 to 80 percent of aluminum sulfate, 1.2 to 8 percent of cryolite, 1 to 5 percent of hydroxycarboxylic acid, 4 to 10 percent of organic alcohol amine, 1 to 5 percent of inorganic acid and the balance of water.
3. The method for producing a liquid accelerator according to claim 2, comprising the steps of:
(1) Mixing water, aluminum sulfate and cryolite, heating to 50-100 ℃, and stirring until the solution is clear;
(2) And (2) adding an aluminum fluoride solution into the clear solution obtained in the step (1), uniformly mixing at the temperature of 50-80 ℃, adding hydroxycarboxylic acid, after completely dissolving, sequentially adding organic alcohol amine and an inorganic acid aqueous solution, and cooling to room temperature to obtain a liquid accelerator product.
4. The process according to claim 3, wherein the cryolite in step (1) is one or a mixture of two or more of a single cryolite, a calcined cryolite and a silica cryolite.
5. The method of claim 3, wherein the aluminum fluoride solution is prepared by:
adding aluminum hydroxide into fluosilicic acid or hydrofluoric acid at the temperature of 80-100 ℃, stirring and dissolving for 30-80 minutes, and filtering to obtain a clear solution to prepare an aluminum fluoride solution.
6. A process according to claim 5, wherein the concentration of the fluorosilicic acid or hydrofluoric acid is from 15wt% to 40wt%.
7. The method according to claim 3, wherein the hydroxycarboxylic acid in the step (2) is one or a mixture of two or more of citric acid, salicylic acid, tartaric acid and lactic acid.
8. The method according to claim 3, wherein the organic alcohol amine in the step (2) is monoethanolamine, diethanolamine or triethanolamine.
9. The preparation method according to claim 3, wherein the inorganic acid in the step (2) is one or a mixture of two or more of hydrofluoric acid, phosphoric acid, nitric acid and sulfuric acid; the concentration of the inorganic acid aqueous solution is 5wt% -15 wt%.
10. Use of the liquid accelerator according to claim 2 for improving the setting properties of concrete.
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| JP2014152056A (en) * | 2013-02-06 | 2014-08-25 | Denki Kagaku Kogyo Kk | Liquid quick-setting agent, quick-settable cement concrete, and spray construction method using the same |
| JP2015231930A (en) * | 2014-06-10 | 2015-12-24 | デンカ株式会社 | Liquid rapid hardening agent, rapid hardening cement concrete and spraying process using the same |
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| CN111153619A (en) * | 2020-01-14 | 2020-05-15 | 攀枝花市吉源科技有限责任公司 | Non-hazardous chemical substance alkali-free accelerator of magnesium aluminum fluoride system and preparation method thereof |
| CN113582573A (en) * | 2021-09-01 | 2021-11-02 | 多氟多新材料股份有限公司 | Accelerating agent and preparation method and application thereof |
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| CN1816501A (en) * | 2003-10-20 | 2006-08-09 | 电气化学工业株式会社 | Liquid quick-setting admixture, shotcreting material and method for shotcreting using them |
| JP2014152056A (en) * | 2013-02-06 | 2014-08-25 | Denki Kagaku Kogyo Kk | Liquid quick-setting agent, quick-settable cement concrete, and spray construction method using the same |
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