CN116462441B - Early-strength fluorine-free alkali-free liquid accelerator and preparation method thereof - Google Patents
Early-strength fluorine-free alkali-free liquid accelerator and preparation method thereof Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000003756 stirring Methods 0.000 claims abstract description 81
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 52
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 21
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 21
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 21
- 239000000375 suspending agent Substances 0.000 claims abstract description 21
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 84
- 238000006243 chemical reaction Methods 0.000 claims description 62
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 17
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 claims description 12
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000011378 shotcrete Substances 0.000 description 13
- 239000004567 concrete Substances 0.000 description 12
- 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 description 10
- 239000003513 alkali Substances 0.000 description 9
- 239000004568 cement Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 sodium (potassium) aluminate Chemical class 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- ZHWKJMGWTPJJRZ-UHFFFAOYSA-I magnesium pentafluoroaluminum(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[Mg++].[Al+3] ZHWKJMGWTPJJRZ-UHFFFAOYSA-I 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
-
- 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
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
-
- 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
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/147—Alkali-metal sulfates; Ammonium sulfate
-
- 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
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/148—Aluminium-sulfate
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an early-strength fluorine-free alkali-free liquid accelerator and a preparation method thereof, wherein the accelerator is prepared from the following components in percentage by weight: 40-52% of polyaluminium sulfate, 3-8% of magnesium sulfate, 5-10% of lithium sulfate, 6-12% of diethanolamine, 1-3% of ethylene glycol, 5-12% of modified nano metakaolin, 1-3% of suspending agent, 1-3% of oxalic acid and the balance of water to 100%; the preparation method of the accelerator comprises the following steps: dissolving polyaluminium sulfate, magnesium sulfate and lithium sulfate in water, and stirring for 1-2 h; keeping the temperature and the stirring speed unchanged, and slowly dripping diethanolamine and glycol within 0.5-1 h; adding modified nano metakaolin and a suspending agent, and stirring for 0.5-1 h; keeping the temperature and the stirring speed unchanged, adding oxalic acid, adjusting the pH value of the solution to 2.0-4.0, and slowly cooling to room temperature to obtain the early-strength fluorine-free alkali-free liquid accelerator.
Description
Technical Field
The invention relates to the field of concrete additives, in particular to an early-strength fluorine-free alkali-free liquid accelerator and a preparation method thereof.
Background
Along with the rapid development of underground engineering and traffic infrastructure construction, the technology of using sprayed concrete to repair slopes, support surrounding rocks and perform plugging and rapid maintenance of tunnel blasting construction is increasingly widely applied.
The sprayed concrete is one kind of concrete produced through mixing cement, aggregate, etc in certain proportion, spraying the mixture to the sprayed surface via compressed air or other power source and adhering the sprayed surface tightly. The construction technology generally does not need templates, can effectively save investment, reduce cost and accelerate construction progress. Due to the special construction process, the existing sprayed concrete is easy to have the problems of high rebound, insufficient initial and later strength, poor impermeability and the like, wastes materials, reduces the service life of the structure, and the ejected or dropped concrete can also cause personal safety hidden trouble of constructors.
The current method for reducing the rebound rate of the sprayed concrete is mainly developed and researched from the aspects of equipment improvement, construction process, concrete mixing ratio, accelerator and the like, and the comprehensive performance of the sprayed concrete is effectively improved. The accelerator is a core additive in sprayed concrete and plays a main role in the setting speed and strength of the concrete, so that the research and development and application of the accelerator are key factors for determining the technical level of the sprayed concrete. The accelerator has various types and can be divided into powder (solid state) and liquid accelerator according to the product form; the liquid accelerator can be classified into high-alkali, low-alkali and alkali-free liquid accelerators according to alkali content, and can be classified into water glass type, sodium (potassium) aluminate type, aluminum sulfate type and sulfur-free alkali-free chlorine-free type according to main coagulation accelerator components. Since the earliest development of Sigunique powder accelerator by Sika company in Switzerland in the 30 th 20 th century, the development of accelerators has undergone several stages of powder high alkali, powder low alkali, liquid high alkali, liquid low alkali, organic polymer compounding and liquid alkali-free. The alkali-free liquid accelerator is an important research direction in the present and future, reduces the possibility of alkali aggregate reaction, and effectively improves the later strength ratio of concrete.
The main component of the alkali-free accelerator is aluminum sulfate (Al 2 (SO 4 ) 3 ) Inorganic or organic acid is usually added into the aqueous solution to keep the components stable and avoid the phenomenon of standing layering. When this type of alkali-free accelerator is incorporated into a cementitious matrix, a significant amount of Al is incorporated 3+ ，SO 4 2- Ion and H + Ions. As the pH in the cement paste is greatly increased compared with the alkali-free accelerator, the Al is promoted 3+ Conversion of ions to [ Al (OH) 4 ] - Ions, then with free Ca in the slurry 2+ And SO 4 2- Ion reaction; at the same time, the incorporation of alkali-free accelerator also helps to increase the sulphate concentration in the slurry liquid phase, AFt being the main hydration product formed in the matrixThe mass formation and growth are the main processes of reducing the solidification time and improving the strength development rate, and compared with the process of adding the alkali accelerator, the method has the advantages of higher later strength retention rate and environmental protection.
Chinese patent document CN201811524609.3 discloses a nano seed crystal enhanced alkali-free accelerator and a preparation method thereof, the accelerator is composed of the following raw materials in parts by mass: 0 to 15 percent of lithium sulfate, 30 to 50 percent of aluminum sulfate, 5 to 10 percent of magnesium sulfate, 5 to 15 percent of modified nano silicon dioxide microspheres, 5 to 10 percent of organic alcohol amine, 3 to 5 percent of inorganic acid and the balance of water; the novel alkali-free accelerator has the outstanding characteristics of low mixing amount, good stability, high strength retention rate, environmental friendliness in production and the like, and can effectively improve the mechanical property and durability of sprayed concrete; however, the modified nano silicon dioxide microspheres have larger specific surface area and surface energy, are difficult to disperse in concrete, and finally can lead to the reduction of the mechanical properties of the concrete.
Chinese patent document CN107337374a provides a fluorine-containing alkali-free liquid accelerator comprising an aqueous magnesium and/or aluminum silicon complex solution of a fluorine-containing compound, and at least one polyhydroxy dispersion enhancing agent; the accelerator has long storage life, excellent quick setting effect on cement-containing cementing materials and long-age strength retention performance.
Due to F in the fluorine-containing compound - For Al 3+ Has extremely strong complexing ability and can improve Al in liquid phase 3+ The content is favorable for increasing the stability of the alkali-free liquid accelerator, so that fluorine-containing compounds such as hydrofluoric acid, sodium fluoride, magnesium fluosilicate, magnesium aluminum fluoride and the like are used in a large amount in the selection of the raw materials of the liquid accelerator. However, the fluorine-containing compound has extremely strong toxicity and corrosiveness, is harmful to the surrounding environment, seriously harms the health of workers on a construction site for a long time, and is extremely unfriendly to the environment.
Disclosure of Invention
In order to solve the defects existing in the prior art, the invention aims to provide an early-strength fluorine-free alkali-free liquid accelerator and a preparation method thereof, which can improve the quick setting effect and mechanical property of sprayed concrete.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the early-strength fluorine-free alkali-free liquid accelerator is prepared from the following components in percentage by weight: 40-52% of polyaluminium sulfate, 3-8% of magnesium sulfate, 5-10% of lithium sulfate, 6-12% of diethanolamine, 1-3% of ethylene glycol, 5-12% of modified nano metakaolin, 1-3% of suspending agent, 1-3% of oxalic acid and the balance of water to 100%;
the modified nano metakaolin is obtained by treating nano metakaolin with KH550, itaconic anhydride and 4-vinylaniline.
Preferably, the preparation method of the modified nano metakaolin comprises the following steps:
(1) Dispersing nano metakaolin in deionized water, then adding KH550, stirring for reaction, and filtering, washing and drying the product after the reaction is finished to obtain aminated nano metakaolin;
(2) Adding itaconic anhydride into N, N-dimethylformamide, and uniformly stirring to obtain itaconic anhydride solution for later use; dispersing aminated nano metakaolin into N, N-dimethylformamide to obtain dispersion liquid, then dripping itaconic anhydride solution into the dispersion liquid, stirring for reaction, and filtering, washing and drying the product after the reaction is finished to obtain functionalized nano metakaolin;
(3) Adding the functionalized nano metakaolin and 4-vinylaniline into N, N-dimethylformamide, uniformly stirring, dripping dibenzoyl peroxide, stirring for reaction, and filtering, washing and drying the product after the reaction is finished to obtain the modified nano metakaolin.
Preferably, in the step (1), the reaction condition is that stirring reaction is carried out for 4-6 hours at 75-90 ℃.
Preferably, in the step (1), the weight ratio volume of nano metakaolin, KH550 and deionized water is 1g:0.5 g to 2g: 10-20 mL.
Preferably, in the step (2), the reaction condition is that stirring reaction is carried out for 4-8 hours at 60-80 ℃.
Preferably, in step (2), the weight fraction of the itaconic anhydride solution is 15 to 25wt%.
Preferably, in the step (2), the weight ratio of the aminated metakaolin, the N, N-dimethylformamide and the itaconic anhydride solution is 1:1.5 to 3:1 to 5.
Preferably, in the step (3), the reaction condition is that stirring reaction is carried out for 3-5 hours at 70-90 ℃.
Preferably, in the step (3), the weight ratio of the functionalized nano metakaolin to the 4-vinylaniline to the N, N-dimethylformamide to the dibenzoyl peroxide is 1:0.5 to 1.2: 5-10: 0.05.
the invention also claims a preparation method of the early-strength fluorine-free alkali-free liquid accelerator, which comprises the following steps:
a. dissolving polyaluminium sulfate, magnesium sulfate and lithium sulfate in water, and stirring for 1-2 h at 55-75 ℃ and 300-500 r/min;
b. keeping the temperature and the stirring speed unchanged, and slowly dripping diethanolamine and glycol within 0.5-1 h;
c. slowly adding the modified nano metakaolin and the suspending agent, and stirring for 0.5-1 h at the temperature of 55-75 ℃ and the speed of 300-500 r/min;
d. keeping the temperature and stirring speed unchanged, slowly adding oxalic acid, regulating the pH value of the solution to 2.0-4.0, and slowly cooling to room temperature to obtain the early-strength fluorine-free alkali-free liquid accelerator.
Compared with the prior art, the invention has the following beneficial effects:
1) The early-strength fluorine-free alkali-free liquid accelerator provided by the invention adopts the aluminum sulfate-magnesium sulfate-lithium sulfate-nano metakaolin multi-component coagulation accelerator, so that the coagulation accelerator is greatly improved, the dosage of the accelerator is reduced, meanwhile, the modified nano metakaolin can effectively overcome the defect of low early strength of the alkali-free fluorine-free liquid accelerator by virtue of the pozzolanic activity, the filling effect and the crystal nucleus effect, and the later strength of cement mortar can be improved.
2) The early-strength fluorine-free alkali-free liquid accelerator provided by the invention does not contain alkaline substances, does not use fluorine-containing compounds, is friendly to human bodies and environment, can accelerate the hydration speed of cement, shortens the setting time, can obviously improve the early strength of sprayed concrete, and does not have adverse effects on the later strength and durability.
3) The early-strength fluorine-free alkali-free liquid accelerator provided by the invention can stably suspend in a concrete material after modifying nano metakaolin, reduce the agglomeration phenomenon in a newly mixed cement-based material, fully exert the filling effect, fill the pores in the concrete, and increase the compactness of the structure; the nano metakaolin has extremely strong volcanic ash activity, can react with calcium hydroxide to generate C-S-H gel, and grows in a space skeleton formed by AFt crystals to play a role in consolidation, so that the mechanical property and durability of the concrete are improved.
4) The early-strength fluorine-free alkali-free liquid accelerator provided by the invention contains various active functional groups such as amide, carboxyl, amino and the like in the modified nano metakaolin, and can be combined with Al through hydrogen bond and complexation 3+ 、Mg 3+ 、Ca 2+ The metal ions act to increase the solubility and stability of the metal ions and promote C 3 The dissolution of A accelerates the formation of ettringite and AFm, thereby remarkably shortening the initial setting and final setting time of the mud; the chemical bonding between the organic functional group and the metal cation is mutually penetrated with the network structure formed by the diethanolamine and the glycol, so that a rich soluble area is formed, the diffusion rate of hydration products is improved, the early strength of the concrete is improved, and the rebound of the sprayed concrete is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
Polyaluminum sulfate is purchased from Henan Aisen environmental protection technology Co., ltd., particle size of 80-100 meshes, al 2 O 3 Content of>25％；
Nanometer metakaolin is purchased from the company of inner Mongolia super brand metakaolin, the median particle diameter is 1.75 mu m, and the thickness of the lamellar layer is 15-70 nm;
the suspending agent is purchased from Dongguan Jianshi New Material technology Co., ltd., model QM168C.
The invention will be further illustrated by the following examples.
Example 1
The preparation method of the modified nano metakaolin comprises the following steps:
(1) Dispersing 10g of nano metakaolin in 200mL of deionized water, then adding 20g of KH550, stirring at 90 ℃ for reaction for 6 hours, and filtering, washing and drying the product after the reaction is finished to obtain aminated nano metakaolin;
(2) 10g of itaconic anhydride is added into 40g of N, N-dimethylformamide, and uniformly stirred to obtain itaconic anhydride solution for standby; dispersing 10g of aminated nano metakaolin into 30g of N, N-dimethylformamide to obtain dispersion liquid, then dripping 50g of itaconic anhydride solution into the dispersion liquid, stirring at 80 ℃ for reaction for 8 hours, and filtering, washing and drying the product after the reaction is finished to obtain the functionalized nano metakaolin;
(3) Adding 10g of functionalized nano metakaolin and 12g of 4-vinylaniline into 100g of N, N-dimethylformamide, uniformly stirring, dripping 0.5g of dibenzoyl peroxide, stirring at 90 ℃ for reaction for 5 hours, filtering the product after the reaction is finished, washing with methanol, and drying to obtain the modified nano metakaolin.
The early-strength fluorine-free alkali-free liquid accelerator is prepared from the following components in percentage by weight: 52% of polyaluminium sulfate, 3% of magnesium sulfate, 5% of lithium sulfate, 6% of diethanolamine, 1% of ethylene glycol, 5% of modified nano metakaolin, 1% of suspending agent, 2% of oxalic acid and the balance of water;
the preparation method of the early-strength fluorine-free alkali-free liquid accelerator comprises the following steps:
a. dissolving the polymeric aluminum sulfate, magnesium sulfate and lithium sulfate in the formula amount in water, and stirring for 2 hours at 75 ℃ and 500 r/min;
b. keeping the temperature and the stirring speed unchanged, slowly dripping the diethanolamine and the glycol in the formula amount within 1 hour;
c. slowly adding the modified nano metakaolin and the suspending agent in the formula amount, and stirring for 1h at 75 ℃ and 500 r/min;
d. keeping the temperature and stirring speed unchanged, slowly adding oxalic acid, adjusting the pH value of the solution to 2.6, and slowly cooling to room temperature to obtain the early-strength fluorine-free alkali-free liquid accelerator.
Example 2
The preparation method of the modified nano metakaolin comprises the following steps:
(1) Dispersing 10g of nano metakaolin in 100mL of deionized water, then adding 5g of KH550, stirring at 75 ℃ for reaction for 4 hours, and filtering, washing and drying the product after the reaction is finished to obtain aminated nano metakaolin;
(2) Adding 2g of itaconic anhydride into 8g of N, N-dimethylformamide, and uniformly stirring to obtain an itaconic anhydride solution for later use; dispersing 10g of aminated nano metakaolin into 15g of N, N-dimethylformamide to obtain dispersion liquid, then dripping 10g of itaconic anhydride solution into the dispersion liquid, stirring at 60 ℃ for reaction for 4 hours, and filtering, washing and drying a product after the reaction is finished to obtain the functionalized nano metakaolin;
(3) Adding 10g of functionalized nano metakaolin and 5g of 4-vinylaniline into 50g of N, N-dimethylformamide, uniformly stirring, dripping 0.5g of dibenzoyl peroxide, stirring at 70 ℃ for reaction for 3 hours, filtering the product after the reaction is finished, washing with methanol, and drying to obtain the modified nano metakaolin.
The early-strength fluorine-free alkali-free liquid accelerator is prepared from the following components in percentage by weight: 40% of polyaluminum sulfate, 8% of magnesium sulfate, 10% of lithium sulfate, 12% of diethanolamine, 3% of ethylene glycol, 12% of modified nano metakaolin, 3% of suspending agent, 2% of oxalic acid and the balance of water;
the preparation method of the early-strength fluorine-free alkali-free liquid accelerator comprises the following steps:
a. dissolving the polymeric aluminum sulfate, magnesium sulfate and lithium sulfate in the formula amount in water, and stirring for 1h at 55 ℃ and 300 r/min;
b. keeping the temperature and the stirring speed unchanged, slowly dripping the diethanolamine and the glycol in the formula amount within 0.5h;
c. slowly adding the modified nano metakaolin and the suspending agent in the formula amount, and stirring for 0.5h at 55 ℃ and 300 r/min;
d. keeping the temperature and stirring speed unchanged, slowly adding oxalic acid, adjusting the pH value of the solution to 2.6, and slowly cooling to room temperature to obtain the early-strength fluorine-free alkali-free liquid accelerator.
Example 3
The preparation method of the modified nano metakaolin comprises the following steps:
(1) Dispersing 10g of nano metakaolin in 120mL of deionized water, then adding 10g of KH550, stirring at 80 ℃ for reaction for 4.5 hours, and filtering, washing and drying the product after the reaction is finished to obtain the aminated nano metakaolin;
(2) Adding 5g of itaconic anhydride into 20g of N, N-dimethylformamide, and uniformly stirring to obtain an itaconic anhydride solution for later use; dispersing 10g of aminated nano metakaolin into 20g of N, N-dimethylformamide to obtain dispersion liquid, then dripping 25g of itaconic anhydride solution into the dispersion liquid, stirring at 65 ℃ for reaction for 5 hours, and filtering, washing and drying a product after the reaction is finished to obtain the functionalized nano metakaolin;
(3) Adding 10g of functionalized nano metakaolin and 8g of 4-vinylaniline into 60g of N, N-dimethylformamide, uniformly stirring, dripping 0.5g of dibenzoyl peroxide, stirring at 75 ℃ for reaction for 3.5h, filtering the product after the reaction, washing with methanol, and drying to obtain the modified nano metakaolin.
The early-strength fluorine-free alkali-free liquid accelerator is prepared from the following components in percentage by weight: 45% of polyaluminum sulfate, 3% of magnesium sulfate, 5% of lithium sulfate, 8% of diethanolamine, 2% of ethylene glycol, 8% of modified nano metakaolin, 2% of suspending agent, 2% of oxalic acid and the balance of water;
the preparation method of the early-strength fluorine-free alkali-free liquid accelerator comprises the following steps:
a. dissolving the polymeric aluminum sulfate, magnesium sulfate and lithium sulfate in the formula amount in water, and stirring for 1.5h at 60 ℃ and 400 r/min;
b. keeping the temperature and the stirring speed unchanged, slowly dripping the diethanolamine and the glycol in the formula amount within 0.6h;
c. slowly adding the modified nano metakaolin and the suspending agent in the formula amount, and stirring for 0.6h at 60 ℃ and 400 r/min;
d. keeping the temperature and stirring speed unchanged, slowly adding oxalic acid, adjusting the pH value of the solution to 2.6, and slowly cooling to room temperature to obtain the early-strength fluorine-free alkali-free liquid accelerator.
Example 4
The preparation method of the modified nano metakaolin comprises the following steps:
(1) Dispersing 10g of nano metakaolin in 180mL of deionized water, then adding 15g of KH550, stirring at 85 ℃ for reaction for 5.5 hours, and filtering, washing and drying the product after the reaction is finished to obtain aminated nano metakaolin;
(2) Adding 7.5g of itaconic anhydride into 30g of N, N-dimethylformamide, and uniformly stirring to obtain an itaconic anhydride solution for later use; dispersing 10g of aminated nano metakaolin into 25g of N, N-dimethylformamide to obtain dispersion liquid, then dripping 37.5g of itaconic anhydride solution into the dispersion liquid, stirring at 75 ℃ for reaction for 7 hours, and filtering, washing and drying the product after the reaction is finished to obtain the functionalized nano metakaolin;
(3) Adding 10g of functionalized nano metakaolin and 10g of 4-vinylaniline into 80g of N, N-dimethylformamide, uniformly stirring, dripping 0.5g of dibenzoyl peroxide, stirring at 85 ℃ for reaction for 4.5h, filtering the product after the reaction, washing with methanol, and drying to obtain the modified nano metakaolin.
The early-strength fluorine-free alkali-free liquid accelerator is prepared from the following components in percentage by weight: 45% of polyaluminum sulfate, 4% of magnesium sulfate, 7% of lithium sulfate, 8% of diethanolamine, 2% of ethylene glycol, 10% of modified nano metakaolin, 2% of suspending agent, 2% of oxalic acid and the balance of water;
the preparation method of the early-strength fluorine-free alkali-free liquid accelerator comprises the following steps:
a. dissolving the polymeric aluminum sulfate, magnesium sulfate and lithium sulfate in the formula amount in water, and stirring for 1.5h at 70 ℃ and 300 r/min;
b. keeping the temperature and the stirring speed unchanged, slowly dripping the diethanolamine and the glycol in the formula amount within 0.8h;
c. slowly adding the modified nano metakaolin and the suspending agent in the formula amount, and stirring for 0.8h at 70 ℃ and 300 r/min;
d. keeping the temperature and stirring speed unchanged, slowly adding oxalic acid, adjusting the pH value of the solution to 2.6, and slowly cooling to room temperature to obtain the early-strength fluorine-free alkali-free liquid accelerator.
Comparative example 1
The preparation method of the modified nano metakaolin comprises the following steps:
(1) 10g of itaconic anhydride is added into 40g of N, N-dimethylformamide, and uniformly stirred to obtain itaconic anhydride solution for standby; dispersing 10g of nano metakaolin into 30g of N, N-dimethylformamide to obtain dispersion liquid, then dripping 50g of itaconic anhydride solution into the dispersion liquid, stirring at 80 ℃ for reaction for 8 hours, and filtering, washing and drying the product after the reaction is finished to obtain the functionalized nano metakaolin;
(2) Adding 10g of functionalized nano metakaolin and 12g of 4-vinylaniline into 100g of N, N-dimethylformamide, uniformly stirring, dripping 0.5g of dibenzoyl peroxide, stirring at 90 ℃ for reaction for 5 hours, filtering the product after the reaction is finished, washing with methanol, and drying to obtain the modified nano metakaolin.
The fluorine-free alkali-free liquid accelerator is prepared from the following components in percentage by weight: 52% of polyaluminium sulfate, 3% of magnesium sulfate, 5% of lithium sulfate, 6% of diethanolamine, 1% of ethylene glycol, 5% of modified nano metakaolin, 1% of suspending agent, 2% of oxalic acid and the balance of water;
the preparation method of the fluorine-free alkali-free liquid accelerator comprises the following steps:
a. dissolving the polymeric aluminum sulfate, magnesium sulfate and lithium sulfate in the formula amount in water, and stirring for 2 hours at 75 ℃ and 500 r/min;
b. keeping the temperature and the stirring speed unchanged, slowly dripping the diethanolamine and the glycol in the formula amount within 1 hour;
c. slowly adding the modified nano metakaolin and the suspending agent in the formula amount, and stirring for 1h at 75 ℃ and 500 r/min;
d. keeping the temperature and stirring speed unchanged, slowly adding oxalic acid, adjusting the pH value of the solution to 2.6, and slowly cooling to room temperature to obtain the fluorine-free alkali-free liquid accelerator.
Comparative example 2
The preparation method of the modified nano metakaolin comprises the following steps:
(1) Dispersing 10g of nano metakaolin in 200mL of deionized water, then adding 20g of KH550, stirring at 90 ℃ for reaction for 6 hours, and filtering, washing and drying the product after the reaction is finished to obtain aminated nano metakaolin;
(2) 10g of amination nanometer metakaolin and 12g of 4-vinylaniline are added into 100g of N, N-dimethylformamide, the mixture is stirred uniformly, 0.5g of dibenzoyl peroxide is dripped into the mixture, the mixture is stirred and reacts for 5 hours at 90 ℃, and after the reaction is finished, the product is filtered, washed by methanol and then dried, so that the modified nanometer metakaolin is obtained.
The fluorine-free alkali-free liquid accelerator is prepared from the following components in percentage by weight: 52% of polyaluminium sulfate, 3% of magnesium sulfate, 5% of lithium sulfate, 6% of diethanolamine, 1% of ethylene glycol, 5% of modified nano metakaolin, 1% of suspending agent, 2% of oxalic acid and the balance of water;
the preparation method of the fluorine-free alkali-free liquid accelerator comprises the following steps:
a. dissolving the polymeric aluminum sulfate, magnesium sulfate and lithium sulfate in the formula amount in water, and stirring for 2 hours at 75 ℃ and 500 r/min;
b. keeping the temperature and the stirring speed unchanged, slowly dripping the diethanolamine and the glycol in the formula amount within 1 hour;
c. slowly adding the modified nano metakaolin and the suspending agent in the formula amount, and stirring for 1h at 75 ℃ and 500 r/min;
d. keeping the temperature and stirring speed unchanged, slowly adding oxalic acid, adjusting the pH value of the solution to 2.6, and slowly cooling to room temperature to obtain the fluorine-free alkali-free liquid accelerator.
Comparative example 3
The preparation method of the functionalized nano metakaolin comprises the following steps:
(1) Dispersing 10g of nano metakaolin in 200mL of deionized water, then adding 20g of KH550, stirring at 90 ℃ for reaction for 6 hours, and filtering, washing and drying the product after the reaction is finished to obtain aminated nano metakaolin;
(2) 10g of itaconic anhydride is added into 40g of N, N-dimethylformamide, and uniformly stirred to obtain itaconic anhydride solution for standby; dispersing 10g of aminated nano metakaolin into 30g of N, N-dimethylformamide to obtain dispersion liquid, then dripping 50g of itaconic anhydride solution into the dispersion liquid, stirring at 80 ℃ for reaction for 8 hours, and filtering, washing and drying the product after the reaction is finished to obtain the functionalized nano metakaolin.
The fluorine-free alkali-free liquid accelerator is prepared from the following components in percentage by weight: 52% of polyaluminium sulfate, 3% of magnesium sulfate, 5% of lithium sulfate, 6% of diethanolamine, 1% of ethylene glycol, 5% of functionalized nano metakaolin, 1% of suspending agent, 2% of oxalic acid and the balance of water;
the preparation method of the fluorine-free alkali-free liquid accelerator comprises the following steps:
a. dissolving the polymeric aluminum sulfate, magnesium sulfate and lithium sulfate in the formula amount in water, and stirring for 2 hours at 75 ℃ and 500 r/min;
b. keeping the temperature and the stirring speed unchanged, slowly dripping the diethanolamine and the glycol in the formula amount within 1 hour;
c. slowly adding the functional nano metakaolin and the suspending agent in the formula amount, and stirring for 1h at 75 ℃ and 500 r/min;
d. keeping the temperature and stirring speed unchanged, slowly adding oxalic acid, adjusting the pH value of the solution to 2.6, and slowly cooling to room temperature to obtain the fluorine-free alkali-free liquid accelerator.
Test case
The fluorine-free alkali-free liquid accelerator prepared in examples 1 to 4 and comparative examples 1 to 3 was added to cement paste, and the cement was standard cement P.I 42.5 (available from Fushun cement Co., ltd.) in an amount of 6%. Basic performances of the accelerator are detected by referring to GB/T35159-2017 accelerator for shotcrete and Q/CR 807-2020 liquid alkali-free accelerator for tunnel shotcrete, and test results are shown in Table 1.
TABLE 1 Performance summary of accelerator
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (2)
1. The early-strength fluorine-free alkali-free liquid accelerator is characterized by comprising the following components in percentage by weight: 40-52% of polyaluminium sulfate, 3-8% of magnesium sulfate, 5-10% of lithium sulfate, 6-12% of diethanolamine, 1-3% of ethylene glycol, 5-12% of modified nano metakaolin, 1-3% of suspending agent, 1-3% of oxalic acid and the balance of water to 100%;
the modified nano metakaolin is obtained by treating nano metakaolin with KH550, itaconic anhydride and 4-vinylaniline;
the preparation method of the modified nano metakaolin comprises the following steps:
(1) Dispersing nano metakaolin in deionized water, then adding KH550, stirring for reaction, and filtering, washing and drying the product after the reaction is finished to obtain aminated nano metakaolin;
(2) Adding itaconic anhydride into N, N-dimethylformamide, and uniformly stirring to obtain itaconic anhydride solution for later use; dispersing aminated nano metakaolin into N, N-dimethylformamide to obtain dispersion liquid, then dripping itaconic anhydride solution into the dispersion liquid, stirring for reaction, and filtering, washing and drying the product after the reaction is finished to obtain functionalized nano metakaolin;
(3) Adding the functionalized nano metakaolin and 4-vinylaniline into N, N-dimethylformamide, uniformly stirring, dripping dibenzoyl peroxide, stirring for reaction, and filtering, washing and drying a product after the reaction is finished to obtain modified nano metakaolin;
in the step (1), the reaction condition is that stirring reaction is carried out for 4 to 6 hours at the temperature of 75 to 90 ℃;
in the step (1), the weight ratio volume of nano metakaolin, KH550 and deionized water is 1g:0.5 g to 2g: 10-20 mL;
in the step (2), the reaction condition is that stirring reaction is carried out for 4 to 8 hours at the temperature of between 60 and 80 ℃;
in the step (2), the weight fraction of the itaconic anhydride solution is 15-25 wt%;
in the step (2), the weight ratio of the aminated metakaolin, the N, N-dimethylformamide and the itaconic anhydride solution is 1:1.5 to 3:1 to 5;
in the step (3), the reaction condition is that stirring reaction is carried out for 3 to 5 hours at the temperature of between 70 and 90 ℃;
in the step (3), the weight ratio of the functionalized nano metakaolin to the 4-vinylaniline to the N, N-dimethylformamide to the dibenzoyl peroxide is 1:0.5 to 1.2: 5-10: 0.05.
2. a method for preparing the early-strength fluorine-free alkali-free liquid accelerator according to claim 1, which is characterized by comprising the following steps:
a. dissolving polyaluminium sulfate, magnesium sulfate and lithium sulfate in water, and stirring for 1-2 h at 55-75 ℃ and 300-500 r/min;
b. keeping the temperature and the stirring speed unchanged, and slowly dripping diethanolamine and glycol within 0.5-1 h;
c. slowly adding the modified nano metakaolin and the suspending agent, and stirring for 0.5-1 h at the temperature of 55-75 ℃ and the speed of 300-500 r/min;
d. keeping the temperature and stirring speed unchanged, slowly adding oxalic acid, regulating the pH value of the solution to 2.0-4.0, and slowly cooling to room temperature to obtain the early-strength fluorine-free alkali-free liquid accelerator.
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