CN109896771A - A kind of alkali-free liquid accelerator and preparation method thereof - Google Patents
A kind of alkali-free liquid accelerator and preparation method thereof Download PDFInfo
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- CN109896771A CN109896771A CN201910339396.5A CN201910339396A CN109896771A CN 109896771 A CN109896771 A CN 109896771A CN 201910339396 A CN201910339396 A CN 201910339396A CN 109896771 A CN109896771 A CN 109896771A
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- alkali
- free liquid
- liquid accelerator
- accelerator
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- 239000007788 liquid Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 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 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 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 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 15
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 100
- 238000003756 stirring Methods 0.000 claims description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000005352 clarification Methods 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 11
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 10
- 229940043237 diethanolamine Drugs 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 5
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229940031098 ethanolamine Drugs 0.000 claims description 4
- NPHFFBWJNRVQNH-UHFFFAOYSA-H NN.S(=O)(=O)([O-])[O-].[Al+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[Al+3] Chemical class NN.S(=O)(=O)([O-])[O-].[Al+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[Al+3] NPHFFBWJNRVQNH-UHFFFAOYSA-H 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- RTPZMMAGRZFGBG-UHFFFAOYSA-N ethanol;propan-2-ol Chemical compound CCO.CCO.CC(C)O RTPZMMAGRZFGBG-UHFFFAOYSA-N 0.000 claims description 3
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 claims description 3
- -1 salt compounds Chemical class 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229960004418 trolamine Drugs 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 31
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000004567 concrete Substances 0.000 description 18
- 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 16
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 239000011378 shotcrete Substances 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- WAKTWVHWRCNIKU-UHFFFAOYSA-N S(=O)(=O)(O)O.[AlH3] Chemical compound S(=O)(=O)(O)O.[AlH3] WAKTWVHWRCNIKU-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LTNAZMHLLGXLST-UHFFFAOYSA-N ethanol;propan-1-ol Chemical compound CCO.CCO.CCCO LTNAZMHLLGXLST-UHFFFAOYSA-N 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 210000000887 face Anatomy 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to alkali-free liquid accelerators, by solution A and solution B, mixed preparing is formed in proportion, by percentage to the quality, the material component for preparing solution A includes 45-60% Patent alum, 0.05-1% sodium fluoride, the solidifying component of the inorganic rush of 2-5%, the organic early strength agent of 2-4% and 35-50% water；The raw material for preparing solution B includes 45-55% Patent alum, 8-15% sodium metaaluminate, the organic early strength agent of 2-4%, 3-6% tackifier and 25-40% water.The stability of solution A and solution B is good, and scene compounds the performance of adjustable accelerator, on the one hand can overcome in work progress because the factors brings such as temperature, cementitious material variation influence, improve it to environmental suitability；On the other hand accelerator can be made to be suitable for a plurality of types of cement.Its materials safety is easy to get, is readily transported, and simple process, easily operated.
Description
Technical field
The present invention relates to accelerator technical fields, in particular to a kind of alkali-free liquid accelerator and preparation method thereof.
Background technique
Accelerator is essential additive in gunite concrete, it makes cement cementitious material first in minutes
Coalescence hardening, can reach final set within more than ten minutes.Exactly accelerator ensure gunite concrete have rapid hardening, it is fast hard,
The performances such as early strong, meet the requirement of special construction technique in engineering construction, are greatly expanded the application neck of gunite concrete
Domain.Therefore, the research and development of new and effective accelerator are always the emphasis of gunite concrete scientific research, by domestic and international concrete research person
Concern.
Powder and two kinds of liquid can be divided into according to the property of accelerator and state.Powder accelerator is not soluble in water, is spraying
It penetrates with the use of powdery spray pattern in concrete, springback capacity is big, construction site dust concentration is very big, be easy to cause environmental pollution
With damage operator's health, and later strength and endurance quality cannot be effectively ensured, the development of powder accelerator and
Using being greatly limited, situation on the verge of being replaced at present.
With the development of concrete-spraying technology, there is liquid accelerator.Liquid accelerator is applied with respect to powder accelerator
Working medium amount is stablized, and durability is good, has apparent performance advantage.Liquid accelerator can be divided into high-alkali, low alkali and nothing by alkali content
Alkali liquid quick-setting agent is promoted solidifying component and can be divided into water glass type, aluminic acid sodium form, sulfuric acid aluminium profiles and without sulphur alkali-free chlorine-free type as main.
Using water glass type and aluminic acid sodium form, as the high alkali liquid quick-setting agent of representative, there are the following problems: 1) 28d compression strength is possessed
Rate is low；2) high alkali content damages the health of builder, also increases the probability that alkali-aggregate reaction occurs, causes concrete resistance to
Long property decline.It is the alkali-free liquid accelerator of representative with its high long-term strength retention, alkali-free chlorine-free, safety using sulfuric acid aluminium profiles
The advantages that environmental protection and high-durability, which is just gradually replacing high alkali liquid quick-setting agent, becomes the direction of liquid accelerator development.
Currently, more well-known alkali-free liquid accelerator belongs to aluminum sulfate system in the world: Italian Mapequick AF
Series, the Sigunite AF series of Sika and BASF Master SA series.Therefore, the research and development of alkali-free liquid setting accelerator are always
Around how improving in accelerator aluminium ion concentration or active aluminum concentration and be stabilized it.Promote solidifying component according to inorganic,
Document (tunnel construction, 2017,37(5), 543-552) disclose the several method of current liquid alkali-free quick-coagulant preparation: sulfuric acid
Aluminium series, aluminum sulfate, aluminium hydroxide series, aluminum sulfate, aluminium hydroxide, hydrofluoric acid series, aluminum sulfate, fluorination magnalium series, sulphur
Sour aluminium, sodium fluoride series.The feature of each series is as follows: aluminum sulfate series accelerator volume is larger, organic complexing agent in accelerator
Volume is big, cost of material and higher operating costs；Although aluminum sulfate, aluminium hydroxide series accelerator have high early strong, low rebound
The advantages that rate, high long-term strength retention, good durability, but activity Al (OH)3Raw material is not easy to obtain, and polyaluminium sulfate is stablized
Property is poor, a large amount of stabilizer need to be added, accelerator is at high cost；Aluminum sulfate, aluminium hydroxide, hydrofluoric acid series accelerator volume be low,
Cement adaptability is good, general early strength growth is relatively slow, later strength is higher, 28d compressive strength rate is greater than 100%；Aluminum sulfate,
Fluorination magnalium series accelerator has many advantages, such as that cement adaptability is good, later strength is higher, how to make to be fluorinated magnalium in addition
The key technology that stable solution is this series is generated with reacting aluminum sulfate；Aluminum sulfate, sodium fluoride series accelerator have production
Simply, raw material is easy to get, at low cost, and alkali content is low, and concrete workability is good, and viscosity increases fastly, and strength development is rapid in 1d age,
The advantages that 28d compressive strength rate is greater than 85%, while the type accelerator is with volume is big, temperature sensitive, adaptability is general
The deficiencies of.
Currently, the alkali-free liquid setting accelerator sold on domestic market is mainly aluminum sulfate, aluminium hydroxide, hydrofluoric acid series speed
Solidifying agent.However, being influenced by following several respects factor, which faces unprecedented challenge: hydrofluoric acid has strong rotten
Corrosion and hypertoxicity, belong to high-risk chemical, careless slightly in operating process, injury will be brought to operator, or even cause
It is residual；Production, the transport of hydrofluoric acid require specific equipment, this carry out the technique can only in specific region, limit
It is in a wide range of interior popularization；In addition, the price of hydrofluoric acid rose steadily since the second half year in 2018, so that the valence of the technique
Lattice advantage is all gone.Therefore, simple process is developed, the high-performance liquid alkali-free quick-coagulant that materials safety is easy to get is compeled in eyebrow
Eyelash.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of alkali-free liquid accelerators and preparation method thereof, at least up to just
Just operation, adaptable purpose.
In order to solve the above technical problems, according to an aspect of the present invention, a kind of liquid accelerator is provided, by solution A and
Mixed preparing forms solution B in proportion, and by percentage to the quality, the material component for preparing solution A includes that 45-60% 18 water closes
Aluminum sulfate, 0.05-1% sodium fluoride, 2-5% are inorganic to promote solidifying component, the organic early strength agent of 2-4% and 35-50% water；Prepare the original of solution B
Material includes 45-55% Patent alum, 8-15% sodium metaaluminate, the organic early strength agent of 2-4%, 3-6% tackifier and 25-40% water.
Further, the inorganic rush coagulates component combination one or more in sulfate-based compound.
Further, the solidifying component of inorganic rush is selected from one of titanium sulfate, zirconium sulfate, cerous sulfate or a variety of groups
It closes.
Further, the sodium metaaluminate is 40%(mass percent) sodium metaaluminate aqueous solution.
Further, organic early strength agent is selected from monoethanolamine, diethanol amine, triethanolamine, triisopropanolamine, different
One of propanol diethanol amine, diisopropanol monoethanolamine or a variety of combinations.
Further, the tackifier be 20%(mass percent) silicon sol solution.
According to another aspect of the present invention, a kind of method preparing aforesaid liquid accelerator is provided, comprising:
Organic early strength agent, sodium fluoride, water and the solidifying component of inorganic rush are mixed, are added ten after stirring to solution clarification by step (1)
Eight hydrazine aluminum sulfates, are warming up to 70-90 DEG C, continue stirring to solution and clarify, obtain solution A after cooling;
Step (2) mixes water, Patent alum and organic early strength agent, and 40% sodium metaaluminate water is added under stirring condition
Solution continues to stir and be warming up to 50-90 DEG C, is down to room temperature after keeping the temperature 0.8-1.5 h, is eventually adding tackifier, stirring condition
Lower reaction obtains solution B;
Step (3), up to alkali-free liquid accelerator after solution A is mixed in proportion with B.
Further, the tackifier are the 20%(mass hundred obtained by sulfuric acid catalysis methyl orthosilicate (TMOS) hydrolysis
Divide ratio) silicon sol solution.
Compared with prior art, the invention has the following advantages:
(1) alkali content of present invention gained accelerator is less than 1%, and chloride ion content is less than 0.1%, according to GB/T 35159-2017
" gunite concrete accelerator " belongs to alkali-free liquid accelerator；When volume is 7%, cement can be made pre-hardening in 4min, in 9min
Final set, 1d compression strength are greater than 7 MPa, and 28d compressive strength rate is greater than 100%, reaches GB/T 35159-2017 " gunite concrete
With accelerator " qualified product requirement.
(2) the raw materials used in the present invention is easy to get safely, is readily transported, and simple process, easily operated, small by territory restriction,
Be conducive to promote on a large scale.
(3) stability of the method for the present invention acquired solution A and solution B is good, can reach 3 months or more, and accelerator can be
Construction site is transported to after compounding is good, is reused after can also being compounded at the construction field (site).In addition, scene compounding, adjustable speed
On the one hand the performance of solidifying agent can overcome in work progress because the factors brings such as temperature, cementitious material variation influence, improve it
To environmental suitability；On the other hand accelerator can be made to be suitable for a plurality of types of cement.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination." a variety of " as described below refer to two or more.
The raw material of alkali-free liquid accelerator forms
By solution A and solution B, mixed preparing forms liquid accelerator in proportion, prepares the raw material of solution A by percentage to the quality
Component include 45-60% Patent alum, 0.05-1% sodium fluoride, 2-5% it is inorganic promote solidifying component, the organic early strength agent of 2-4% and
35-50% water；Prepare solution B raw material include 45-55% Patent alum, 8-15% sodium metaaluminate, 2-4% organic morning it is strong
Agent, 3-6% tackifier and 25-40% water.
The solution A and solution B can arbitrarily mass ratio mix, such as 2:3,1:1,3:2 etc..
The feature of alkali-free liquid accelerator of the present invention, design is as follows:
Aluminum sulfate: as the base-material of accelerator, the aluminium ion ionized out can be swapped out hydrated calcium silicate gel (C-S-H) diffusion
Calcium ion in layer reduces thickness of diffusion layer, and colloid electric potential reduces, and strengthens the cohesion of Cement-water System, thus
Accelerate the condensation of cement；In addition, the calcium ion that its sulfate ion ionized out can be generated with hydrated cementitious forms high activity
Secondary gypsum (CaSO4·2H2O), secondary gypsum again with cement component tricalcium aluminate (C3A it) reacts rapidly and generates fine needle column
The ettringite of shape, these nascent crystals increase, develop, and network structure is intersected to form between cement granules and accelerates the solidifying of cement
Knot.
Sodium fluoride: on the one hand, it is difficult that the calcium ion that the fluorine ion that sodium fluoride ionizes out can be generated with hydrated cementitious reacts generation
Dissolved salt calcirm-fluoride (CaF2), accelerate cement component tricalcium silicate (C3S dissolution), to accelerate the condensation of cement and improve early stage
Intensity；On the other hand, fluorine ion, can be with Al as excellent coordination ion3+Stable complex compound is formed, high concentration sulphur is improved
The stability of sour aluminum solutions.
Organic early strength agent: selecting alcamine compound, such as: monoethanolamine, diethanol amine, triethanolamine, three isopropanols
One of amine, isopropanol diethanol amine, diisopropanol monoethanolamine or a variety of combinations.Due to the presence of nitrogen, component tool
There is stronger coordination ability, it can be with Al3+Stable complex compound is formed, the stability of high-concentration sulfuric acid aluminum solutions is improved；In addition,
Such compound energy photocatalytic cements aquation accelerates cement hydration process, improves the early strength of concrete.
Sodium metaaluminate: 40%(mass percent concentration is preferably used) sodium metaaluminate aqueous solution.Aluminum sulfate solution is acidity
System can generate active aluminium hydroxide, active hydroxide after the meta-aluminic acid acid sodium solution of alkalinity is added in aluminum sulfate solution
Aluminium and the polyaluminium sulfate high with excessive reacting aluminum sulfate in-situ preparation aluminium content, to improve aluminum ions in solution contain
Amount.
Inorganic to promote solidifying component: the cation of these sulfate has charge more higher than aluminium ion, can improve cement-rapidly
The ionic strength of aqueous systems reduces colloid thickness of diffusion layer, enhancing to generate strong compression to cement colloid diffusion layer
Cohesion between cement colloid, the final condensation hardening for accelerating cement.Preferably, inorganic to promote solidifying component selected from titanium sulfate, sulphur
One of sour zirconium, cerous sulfate or a variety of combinations.
Tackifier: preferably use 20%(mass percent concentration) silicon sol solution, it pass through the positive silicic acid first of sulfuric acid catalysis
Ester (TMOS) hydrolysis obtains.The viscosity of accelerator can be improved, reduce rebound of shotcrete rate；Silica gel is nanoscale silicon
Particle can be filled into the hole of cementitious material, improve the intensity of concrete；In addition, being produced in methyl orthosilicate hydrolytic process
Raw methanol is cement early strength agent, can improve the early strength of concrete.
According to the present embodiment, the stability of solution A and solution B is good, can reach 3 months or more.In addition, solution A and
Solution B can individually be come as accelerator using but volume is larger, and volume can be only achieved GB/T 35159- when being 9%
The qualified product of 2017 " gunite concrete accelerators ", this is because: for solution A, although sodium fluoride, the solidifying component of inorganic rush are all
Can accelerate the condensation of cement to a certain extent, but its mainly promote it is solidifying component -- sulfuric acid aluminium content is lower so that it only exists
Compared with the effect for being just able to achieve acceleration cement setting under large dosage；With solution A on the contrary, the aluminium content of B is higher, however by solubility shadow
It rings, the solidifying component of inorganic rush can not be added in B, this is but also it is excessive as the volume of accelerator.After the two is mixed, gained
Accelerator has a high aluminium content, and have it is a certain amount of it is inorganic promote solidifying component so that its under compared with low-dosage (7%) just
The requirement of GB/T 35159-2017 qualified product can be reached.
Preparation method
The method of liquid accelerator of the present invention, comprising the following steps:
Organic early strength agent, sodium fluoride, water and the solidifying component of inorganic rush are mixed, are added ten after stirring to solution clarification by step (1)
Eight hydrazine aluminum sulfates, are warming up to 70-90 DEG C, continue stirring to solution and clarify, obtain solution A after cooling;
Step (2) mixes water, Patent alum and organic early strength agent, and 40% sodium metaaluminate water is added under stirring condition
Solution continues to stir and be warming up to 50-90 DEG C, is down to room temperature after keeping the temperature 0.8-1.5 h, is eventually adding tackifier, stirring condition
Lower reaction obtains solution B;
Step (3), up to alkali-free liquid accelerator after solution A is mixed in proportion with B.
The tackifier are the 20%(mass percent for passing through sulfuric acid catalysis methyl orthosilicate (TMOS) hydrolysis and obtaining) silicon is molten
Sol solution.It is opposite specifically water and methyl orthosilicate are added in a kettle, be added with stirring concentrated sulfuric acid regulation system pH=
2.0, continue to stir obtained 20% silicon sol solution of 1.5 h at room temperature.
In the present embodiment, it is only necessary to which the mixed proportion for adjusting solution A and solution B can be realized to accelerator performance
Regulation, to make the better adaptability of product.After solution A and solution B mixing, inorganic rush in solution A coagulate component can with it is molten
Tackifier in liquid B react, and generate the metal-oxygen SiClx nano composite oxide colloidal sol of high activity, and this colloidal sol can be
It is precipitated out rapidly in Cement-water System, provides crystal seed for hydrolysis product of cement, accelerate condensation-hardening process of cement.It is logical
Overregulate solution A, the ratio of B, thus it is possible to vary this high activity metal-silica nano composite oxide colloidal sol in accelerator
Content and property, to realize the regulation to accelerator property.
Embodiment
The preparation of 20% silicon sol solution.The water of 31kg and the methyl orthosilicate of 69kg are added in a kettle, stirring is lower to be added
Enter concentrated sulfuric acid regulation system pH=2.0, continuing to stir 1.5 h mass percent concentration is made at room temperature is 20% silicon sol solution.
Following example 1-5 is all made of above-mentioned silicon sol solution.
Embodiment 1
50kg water, 2kg triethanolamine, 1kg sodium fluoride, 2kg zirconium sulfate are added in reactor, added after stirring to solution clarification
Enter 45kg Patent alum, be warming up to 90 DEG C, after continuing stirring to solution clarification, temperature of reactor obtains after dropping to room temperature
Solution A;
36.5kg water, 3kg triethanolamine, 45kg Patent alum are added in reactor, under stirring, by the inclined aluminium of 12.5kg
Acid sodium solution (40%) is slowly added into reactor, continues to stir 20 min, it is clear to solution to then raise temperature to 50 DEG C of 1 h of holding
Clearly, it is then cooled to room temperature, 3kg20% silicon sol solution is added, obtains solution B after stirring 30 min;
Solution A, B 2:3,1:1,3:2 in mass ratio are mixed, alkali-free liquid accelerator 1-1,1-2,1-3 are obtained.
Embodiment 2
45kg water, 2kg ethanol amine, 1kg sodium fluoride, 2kg titanium sulfate are added in reactor, are added after stirring to solution clarification
50kg Patent alum is warming up to 85 DEG C, and after continuing stirring to solution clarification, temperature of reactor obtains solution after dropping to room temperature
A;
32kg water, 3kg triethanolamine, 50kg Patent alum are added in reactor, under stirring, by 10kg sodium metaaluminate
Solution (40%) is slowly added into reactor, continues to stir 20 min, is then raised temperature to 70 DEG C of 1 h of holding and is clarified to solution, connects
Be cooled to room temperature, 5kg20% silicon sol solution is added, stirs after 30 min to obtain solution B;
Solution A, B 2:3,1:1,3:2 in mass ratio are mixed, alkali-free liquid accelerator 2-1,2-2,2-3 are obtained.
Embodiment 3
36kg water, 4kg ethanol amine, 1kg sodium fluoride, 2kg cerous sulfate are added in reactor, are added after stirring to solution clarification
57kg Patent alum is warming up to 80 DEG C, after continuing stirring to solution clarification, temperature of reactor drop to after room temperature obtain it is molten
Liquid A;
28kg water, 3kg triisopropanolamine, 55kg Patent alum are added in reactor, under stirring, by 8kg meta-aluminic acid
Sodium solution (40%) is slowly added into reactor, continue stir 20 min, then raise temperature to 70 DEG C of 1 h of holdings to solution clarification,
Then it is cooled to room temperature, 6kg20% silicon sol solution is added, obtains solution B after stirring 30 min;
Solution A, B 2:3,1:1,3:2 in mass ratio are mixed, alkali-free liquid accelerator 3-1,3-2,3-3 are obtained.
Embodiment 4
35kg water, 3kg diethanol amine, 0.05kg sodium fluoride, 5kg cerous sulfate are added in reactor, stirring to solution is clarified
56.95kg Patent alum is added afterwards, is warming up to 70 DEG C, after continuing stirring to solution clarification, temperature of reactor drops to room
Solution A is obtained after temperature;
25kg water, 2kg isopropanol diethanol amine, 52kg Patent alum are added in reactor, it is under stirring, 15kg is inclined
Sodium aluminate solution (40%) is slowly added into reactor, is continued to stir 20 min, is then raised temperature to 50 DEG C of 0.8 h of holding to molten
Liquid clarification, is then cooled to room temperature, and 6kg20% silicon sol solution is added, and obtains solution B after stirring 30 min;
Solution A, B 2:3,1:1,3:2 in mass ratio are mixed.
Embodiment 5
35kg water, 2.5kg ethanol amine, 0.5kg sodium fluoride, 2kg titanium sulfate are added in reactor, after stirring to solution clarification
60kg Patent alum is added, is warming up to 90 DEG C, after continuing stirring to solution clarification, temperature of reactor obtains after dropping to room temperature
Obtain solution A;
40kg water, 4kg diethanol amine, 45kg Patent alum are added in reactor, under stirring, by 8kg sodium metaaluminate
Solution (40%) is slowly added into reactor, continue stir 20 min, then raise temperature to 90 DEG C of 1.5 h of holdings to solution clarification,
Then it is cooled to room temperature, 3kg20% silicon sol solution is added, obtains solution B after stirring 30 min;
Solution A, B 2:3,1:1,3:2 in mass ratio are mixed.
Test experience 1
According to the method for GB/T 35159-2017 " gunite concrete accelerator ", using 42.5 reference cement of PI, to institute
It obtains alkali-free liquid accelerator and carries out cement paste setting time and cement mortar strength experiment.Wherein accelerator dosage is cement weight
7%, testing result is as shown in table 1.
1 testing result of table
It can be seen that accelerator obtained by the present invention from the data in table 1 and belong to alkali-free liquid accelerator, can effectively shorten cement
Initial set and final setting time, 1d compression strength be greater than 6MPa, 28d compressive strength rate be greater than 80%, meet GB/T 35159-2017
The requirement of qualified product in " gunite concrete accelerator ".The solidifying effect of the rush of gained accelerator after it can also be seen that mixing in table 1
Fruit is substantially better than effect when A, B are used alone.
Test experience 2
To fully understand the resulting alkali-free liquid accelerator of the present invention to the adaptability of different brands cement products, according to GB/T
The method of 35159-2017 " gunite concrete accelerator " selects commercially available common China Resources respectively, Hu Ying, conch, praises China, is red
Lion board P.042.5 ordinary portland cement, to alkali-free liquid accelerator prepared by embodiment 3 carry out cement paste setting time and
Cement mortar strength experiment.Wherein accelerator dosage is the 7% of cement weight, and testing result is as shown in table 2.
2 testing result of table
As shown in Table 2, when the volume of present invention gained alkali-free liquid accelerator is 7%, when the net slurry of various brands cement products condenses
Between and mortar strength can achieve the requirement of qualified product in GB/T 35159-2017 " gunite concrete accelerator ", illustrate this
Invention gained alkali-free liquid accelerator has well adapting to property to cement.
Claims (8)
1. a kind of alkali-free liquid accelerator, it is characterised in that: by solution A and solution B, mixed preparing is formed in proportion, with quality hundred
Point than meter, prepare solution A material component include 45-60% Patent alum, 0.05-1% sodium fluoride, 2-5% it is inorganic promote it is solidifying
The organic early strength agent of component, 2-4% and 35-50% water；The raw material for preparing solution B includes 45-55% Patent alum, 8-15% inclined
The organic early strength agent of sodium aluminate, 2-4%, 3-6% tackifier and 25-40% water.
2. alkali-free liquid accelerator according to claim 1, it is characterised in that: the inorganic rush coagulates component and is selected from sulfuric acid
One or more combination in salt compounds.
3. alkali-free liquid accelerator according to claim 1 or claim 2, it is characterised in that: the inorganic solidifying component of rush is selected from sulfuric acid
One of titanium, zirconium sulfate, cerous sulfate or a variety of combinations.
4. alkali-free liquid accelerator according to claim 1 or 2, it is characterised in that: the sodium metaaluminate is 40%(matter
Measure percentage) sodium metaaluminate aqueous solution.
5. alkali-free liquid accelerator according to claim 1 or 2, it is characterised in that: organic early strength agent is selected from single
One of ethanol amine, diethanol amine, triethanolamine, triisopropanolamine, isopropanol diethanol amine, diisopropanol monoethanolamine or
A variety of combinations.
6. alkali-free liquid accelerator according to claim 1 or 2, it is characterised in that: the tackifier are 20%(mass
Percentage) silicon sol solution.
7. the method for preparing the alkali-free liquid accelerator as described in any one of claim 1-6 characterized by comprising
Organic early strength agent, sodium fluoride, water and the solidifying component of inorganic rush are mixed, are added ten after stirring to solution clarification by step (1)
Eight hydrazine aluminum sulfates, are warming up to 70-90 DEG C, continue stirring to solution and clarify, obtain solution A after cooling;
Step (2) mixes water, Patent alum and organic early strength agent, and 40% sodium metaaluminate water is added under stirring condition
Solution continues to stir and be warming up to 50-90 DEG C, is down to room temperature after keeping the temperature 0.8-1.5 h, is eventually adding tackifier, stirring condition
Lower reaction obtains solution B;
Step (3), up to alkali-free liquid accelerator after solution A is mixed in proportion with B.
8. the method according to claim 7 for preparing alkali-free liquid accelerator, it is characterised in that: the tackifier are to pass through
The 20%(mass percent that sulfuric acid catalysis methyl orthosilicate (TMOS) hydrolysis obtains) silica aqueous solution.
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| CN113860787A (en) * | 2021-02-01 | 2021-12-31 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Double-component alkali-free accelerator suitable for plateau cold regions and use method thereof |
| CN113860787B (en) * | 2021-02-01 | 2022-06-28 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Double-component alkali-free accelerator suitable for plateau cold regions and use method thereof |
| CN113135689A (en) * | 2021-05-29 | 2021-07-20 | 石家庄市长安育才建材有限公司 | Elasticity-reducing low-sulfur alkali-free liquid accelerator and preparation method thereof |
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