CN111056762A - Alkali-free liquid accelerator and preparation method thereof - Google Patents
Alkali-free liquid accelerator and preparation method thereof Download PDFInfo
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- CN111056762A CN111056762A CN201911282319.7A CN201911282319A CN111056762A CN 111056762 A CN111056762 A CN 111056762A CN 201911282319 A CN201911282319 A CN 201911282319A CN 111056762 A CN111056762 A CN 111056762A
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- alkali
- free liquid
- liquid accelerator
- sepiolite
- prepared
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- 239000007788 liquid Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004113 Sepiolite Substances 0.000 claims abstract description 57
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 57
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 57
- 239000000725 suspension Substances 0.000 claims abstract description 38
- -1 alcohol amine Chemical class 0.000 claims abstract description 27
- 229920002310 Welan gum Polymers 0.000 claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 12
- 239000011790 ferrous sulphate Substances 0.000 claims description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- 235000013024 sodium fluoride Nutrition 0.000 claims description 12
- 239000011775 sodium fluoride Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004568 cement Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011378 shotcrete Substances 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 41
- 230000000694 effects Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 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 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 230000002411 adverse Effects 0.000 description 3
- 239000011083 cement mortar Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000002528 anti-freeze Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000004913 activation 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
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000004044 tetrasaccharides Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses an alkali-free liquid accelerator and a preparation method thereof, wherein the alkali-free liquid accelerator comprises, by weight, 40-62% of polyaluminium sulfate, 7-14% of organic alcohol amine, 5-10% of a synergist, 23-33% of a modified suspension and 3% of a pH regulator; wherein, the modified suspension is prepared by mixing the welan gum, the acid-treated sepiolite and the cross-linking agent according to a special proportion. The finally prepared alkali-free liquid accelerator has good stability, can not generate crystallization and layering phenomena after long-term storage, and obviously improves the compressive strength of the sprayed concrete by adopting smaller doping amount.
Description
Technical Field
The invention belongs to the field of production and preparation of sprayed concrete accelerators, and particularly relates to an alkali-free liquid accelerator and a preparation method thereof.
Background
Compared with the traditional support, the shotcrete support has the advantages of simple construction, low cost, fast construction progress and the like, and is widely applied to the shotcrete support of projects such as tunnels, wellways, slope protection and the like. The accelerating agent is used as an additive capable of enabling cement mortar or concrete to be rapidly set and hardened, and is widely applied to sprayed concrete.
The accelerators are classified into basic powder accelerators, alkali-free powder accelerators, basic liquid accelerators and alkali-free liquid accelerators according to physical forms and alkali contents. Along with the development of a spraying process, the liquid accelerator gradually replaces the powder accelerator to occupy the market leading position due to the advantages of uniform mixing, small resilience, uniform spraying quality and the like, and meanwhile, the liquid accelerator increasingly pays more attention to the quality and construction safety of tunnel engineering. The alkali-free liquid accelerator is widely researched due to the advantages of low alkali content, high later strength, small corrosivity to human bodies and the like; but the problems of high mixing amount, poor stability and the like also seriously restrict the popularization and application of the alkali-free liquid accelerator. The alkali-free liquid accelerator applied at present is mainly prepared by adding coordination agents such as organic amine, alcohol amine, organic carboxylic acid, polyhydric alcohol and the like, inorganic raw materials such as fluoride, inorganic acid, magnesium sulfate and the like, and a proper amount of stabilizing agent and viscosity modifier on the basis of aluminum salt. The accelerator is mainly characterized in that the solubility of aluminum salt is improved by using a coordination agent, so that excellent accelerating performance is obtained, the higher the aluminum ion concentration is, the better the accelerating effect is, but the aluminum ion solubility at normal temperature is limited, and the overhigh aluminum salt content often influences the stability of a system, so that the liquid accelerator is crystallized and layered, and finally has adverse effects on actual engineering application, and therefore, the high-activity aluminum ion concentration and the good system stability are the key for preparing the high-performance alkali-free liquid accelerator. Therefore, the development of the liquid accelerator with high effective solid content and good stability is of great significance.
In the prior art, for example, patent CN109678388A provides an antifreeze alkali-free liquid accelerator, which uses aluminum sulfate, aluminum hydroxide, hydrofluoric acid, magnesium salt, alcohol amine, stabilizer, antifreeze component, and water as raw materials, and the stabilizer is one of welan gum, nonionic polyacrylamide, and EDTA. However, the stability of the accelerator is still relatively low, and the accelerator is easy to crystallize and delaminate in a prepared concrete system. The patent CN108793806A provides an alkali-free liquid accelerator, which comprises aluminum sulfate, aluminum hydroxide, phosphoric acid, diethanolamine, glycolic acid, sepiolite ore powder, bisphenol condensate and deionized water, wherein the sepiolite ore powder can form a cross-linked network structure, which is beneficial to increase the liquid viscosity and increase the crystallization resistance of aluminum sulfate. However, the patent does not disclose the specific storage stability period, and the technical effects of the 28d compressive strength ratio and the 90d compressive strength ratio are still in a room for improvement when the 1d compressive strength is measured. For example, patent CN109437646A provides an emulsion type accelerator special for shotcrete, in which activated sepiolite is used, and discloses that the activated sepiolite is prepared by carrying out hydrothermal stirring reaction on sepiolite and dilute hydrochloric acid for 3-5 hours, then carrying out suction filtration, drying and roasting; the sepiolite is subjected to activation treatment, so that the sepiolite can be dispersed fully to form a suspension with good rheological property in the preparation and storage processes of the product, sedimentation is avoided, a micro-expansion hydration product is formed in use, and the later strength is improved. However, the invention does not deeply research how to further improve the storage stability of the alkali-free liquid setting accelerator, and the initial setting time, the final setting time and the 1d compressive strength are not measured, and the 28d compressive strength ratio and the 90d compressive strength ratio are not compared and researched. In conclusion, the prior art still has rising space for the technical effect of the alkali-free liquid accelerator and the corresponding technical parameters. Patent CN108774014A discloses a modified sepiolite stabilizer for liquid accelerator, but the stabilizer still mainly depends on the adsorption and hydrogen bonding between sepiolite and other raw materials, and although sodium silicate is added as a cross-linking agent, no cross-linking reaction occurs with other raw materials, so the final stability still has room for improvement.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the alkali-free liquid accelerator, which greatly prolongs the storage stability of the prepared alkali-free accelerator and is realized by the following technology.
An alkali-free liquid accelerator comprises, by weight, 40-62% of polyaluminium sulfate, 7-14% of organic alcohol amine, 5-10% of a synergist, 23-33% of a modified suspension and 3% of a pH regulator;
the preparation method of the modified suspension comprises the following steps:
s1, stirring and dispersing the welan gum and water at the temperature of 45-55 ℃ for 0.5-1h according to the weight ratio of 1.5-3:100, adding a persulfate initiator, and keeping the temperature for 10-20min to obtain a mixed solution I;
s2, adding the acidized sepiolite and the cross-linking agent into water, and shearing at a high speed of 2000rpm at 1000 for 10-20min to obtain a mixed solution II, wherein the weight ratio of the total weight of the acidized sepiolite and the cross-linking agent to the water is 1: 10;
s3, dropwise adding the mixed solution II into the mixed solution I, and keeping the temperature at 50-65 ℃ for 0.5-1.5h after the dropwise adding is finished.
In the alkali-free liquid accelerator, polyaluminium sulfate with high active aluminum ion content is used as a main accelerating component. The organic alcohol amine is used as a secondary coagulation promoting component, and has a coordination effect, so that the dissolution of polyaluminium sulfate can be promoted, and the concentration of active aluminum ions in the solution can be improved. On the basis, the synergist can further promote the setting and hardening of the sprayed concrete prepared by the alkali-free liquid accelerator and improve the strength of the sprayed concrete. The pH regulator is used for maintaining the acidic environment of the system and preventing the aluminum salt from hydrolysis. The most key raw material is modified suspension prepared from raw materials such as welan gum, acidized sepiolite and the like. The modified suspension liquid forms an interpenetrating network suspension structure in a liquid accelerator system, and prevents the accelerator from crystallizing and layering. The persulfate initiator can be selected from common inorganic salts containing persulfate ions, such as sodium persulfate, potassium persulfate, ammonium persulfate and the like.
In the alkali-free liquid accelerator, the network suspension structure formed by the modified suspension liquid of the mild wheel rubber and the acidized sepiolite depends on physical adsorption and hydrogen bonds, and the mild wheel rubber and the acidized sepiolite can further generate polymerization reaction after the cross-linking agent is added to form a covalent bond, so that the network structure is firmer. The crosslinking agents used are the crosslinking agents which are customary in the market.
Preferably, the alkali-free liquid accelerator comprises 52% of polyaluminium sulfate, 10% of organic alcohol amine, 8% of synergist, 28% of modified suspension and 2% of pH regulator by weight.
Preferably, the weight ratio of the acidized sepiolite to the welan gum is 1: 0.5-1.5; the dosage of the persulfate initiator is 0.5 to 1.5 percent of the total weight of the acidized sepiolite and the rubber wheel; the cross-linking agent is at least one of organic compounds containing a plurality of unsaturated double bonds in the molecule, and the dosage of the cross-linking agent is 0.6-1.2 percent of the total weight of the acidized sepiolite and the rubber cement.
More preferably, the crosslinking agent is at least one of divinylbenzene, diisocyanate and N, N-methylenebisacrylamide.
Preferably, the preparation method of the acidized sepiolite comprises the following steps: adding sepiolite into 13-20% sulfuric acid at 50-75 deg.C, soaking for 12-24 hr, filtering, and oven drying. Common sepiolite is acidified by hydrochloric acid and nitric acid, but the hydrochloric acid contains chloride ions, so that reinforcing steel bars are easily corroded in concrete; nitric acid has a boiling point that is too low (about 78 deg.C) and is too volatile under the acidification conditions of sepiolite (50-75 deg.C). Therefore, the sulfuric acid with high boiling point and without chloride ions is selected.
More preferably, the weight ratio of sepiolite to sulfuric acid is from 4 to 7: 100.
In the modified suspension, the sepiolite has the transition type structural characteristics of chain and layered fiber, and after high-temperature acidification baking, the surface has a large amount of Si-OH capable of participating in reaction, and the interlayer spacing is widened. The welan gum is a bio-based high molecular polymer, consists of tetrasaccharide repeating units, can form a regular spiral net structure after being dissolved in water, and has extremely high thickening performance and unique shearing and diluting performance. The sepiolite acidized by the method is combined with the rubber cement to form an interpenetrating network structure, so that the crystallization and delamination of the setting accelerator can be effectively prevented.
Preferably, in step S3, the dropping time is 20-40 min.
Preferably, the synergist is formed by mixing acid silica sol, sodium fluoride and ferrous sulfate, and the composite proportion is (0.2-1): 0.04-0.5): 1. In the raw materials of the synergist, the acidic silica sol is a common acidic silicic acid hydrosol with the pH value of 2-4, the early strength and the later strength of a sprayed concrete system can be improved, and the sodium fluoride and the ferrous sulfate can promote the coagulation and hardening of the system.
Preferably, the organic alcohol amine is at least one of diethanolamine, triethanolamine and triisopropanolamine; the pH regulator is at least one of phosphoric acid, tartaric acid, salicylic acid and citric acid.
The invention also provides a preparation method of the alkali-free liquid accelerator, which comprises the following steps:
p1, adding organic alcohol amine into the modified suspension at 50-60 ℃ and stirring for 5-10min at the rotation speed of 130-250 rpm;
p2, adding half of the polyaluminium sulfate, continuously stirring for 10-15min, adding the synergist and the other half of the polyaluminium sulfate, and reacting for 1.5-3 h;
p3, adding a pH regulator, and stirring for 20-40min to obtain the finished product of the alkali-free liquid accelerator.
In the preparation method, the polyaluminium sulfate is added in 2 steps in the step P2, so that the stability of the final accelerator can be further improved besides the dispersed dissolution. The reason is that the aluminum ions, the hydramine, the fluorine ions in the synergist, the ferrous ions and the like can form complexes, the feeding modes are different, the complexing modes of the product are different, and tests show that the stability of the product is better when the polymeric aluminum sulfate is fed in batches than when the polymeric aluminum sulfate is fed in one batch.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the modified suspension is prepared by mixing the warm wheel rubber and the acidized sepiolite and is applied to the preparation of the liquid accelerator, so that an interpenetrating network structure is formed while the viscosity of the accelerator system is improved, the aluminum salt is prevented from crystallizing and settling, the stability of the accelerator is greatly improved, and the storage stability of the prepared accelerator can reach more than 12 months.
2. The accelerator is synthesized by introducing the synergist, so that the cement is promoted to be coagulated and hardened, the strength of the hardened cement slurry is improved, the prepared accelerator meets the national standard accelerator for sprayed concrete (GB/T15359-2017), when the mixing amount is 5 percent, the 1d strength is up to more than 17MPa, the 28d compressive strength ratio is more than 120 percent, and the 90d compressive strength retention rate is up to 120 percent.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following examples and comparative examples, unless otherwise specified, were prepared using the following starting materials:
the cross-linking agent is N, N-methylene bisacrylamide; the organic alcohol amine is diethanolamine; the pH regulator is phosphoric acid. The synergist is prepared by mixing acidic silica sol, sodium fluoride and ferrous sulfate, and the compounding ratio is 1:0.5: 1.
Example 1
The alkali-free liquid accelerator prepared in this embodiment includes, by weight, 52% of polyaluminium sulfate, 10% of organic alcohol amine, 8% of a synergist, 28% of a modified suspension, and 2% of a pH adjusting agent;
the modified suspension used in this example was prepared by the following method:
(1) stirring and dispersing 20g of welan gum and 2000g of water at 50 ℃ for 1h, adding 0.4g of sodium persulfate, and keeping the temperature for 15min to obtain a mixed solution I;
(2) adding 50g of sepiolite into 1000g of 13-20% sulfuric acid at 50-75 ℃, soaking for 12h, performing suction filtration and drying to obtain acidized sepiolite;
(3) adding 20g of acidized sepiolite and 0.4g of cross-linking agent into 204mL of water, and shearing at a high speed of 1500rpm for 15min to obtain a mixed solution II;
(4) and dropwise adding the mixed solution II into the mixed solution I, and keeping the temperature at 55 ℃ for 1h after the dropwise adding is slowly completed.
The synergist used in the embodiment is prepared by mixing acidic silica sol, sodium fluoride and ferrous sulfate according to the mass ratio of 1:0.5: 1.
The preparation method of the alkali-free liquid accelerator provided by the embodiment comprises the following steps:
p1, adding organic alcohol amine into the modified suspension liquid at 55 ℃ and stirring for 8min, wherein the rotation speed is 130-250 rpm;
p2, adding half of the polyaluminium sulfate, continuously stirring for 10-15min, adding the synergist and the other half of the polyaluminium sulfate, and reacting for 1.5-3 h;
p3, adding a pH regulator, and stirring for 20-40min to obtain the finished product of the alkali-free liquid accelerator.
Example 2
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: the composite material comprises, by weight, 40% of polyaluminium sulfate, 14% of organic alcohol amine, 10% of a synergist, 33% of a modified suspension and 3% of a pH regulator.
Example 3
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: the composite material comprises, by weight, 62% of polyaluminium sulfate, 7% of organic alcohol amine, 5% of a synergist, 23% of a modified suspension and 3% of a pH regulator.
Example 4
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: in the preparation method of the modified suspension, the acidized sepiolite accounts for 40g, and the welan gum accounts for 20g, namely the weight ratio of the acidized sepiolite to the welan gum is 1: 0.5.
Example 5
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: in the preparation method of the modified suspension, the acidized sepiolite accounts for 20g, and the welan gum accounts for 30g, namely the weight ratio of the acidized sepiolite to the welan gum is 1: 1.5.
Example 6
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: in the preparation method of the modified suspension, the amount of sodium persulfate is 0.2g, namely accounting for 0.5 percent of the total weight of the acidized sepiolite and the welan gum.
Example 7
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: in the preparation method of the modified suspension, the amount of sodium persulfate is 0.6g, namely accounting for 1.5 percent of the total weight of the acidized sepiolite and the welan gum.
Example 8
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: in the preparation method of the modified suspension, the dosage of the N, N' -methylene bisacrylamide is 0.24g, namely accounting for 0.6 percent of the total weight of the acidized sepiolite and the welan gum.
Example 9
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: in the preparation method of the modified suspension, the dosage of the N, N' -methylene bisacrylamide is 0.48g, which is 1.2 percent of the total weight of the acidized sepiolite and the welan gum.
Example 10
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: the synergist is prepared by mixing acidic silica sol, sodium fluoride and ferrous sulfate, and the compounding ratio is 0.2:0.04: 1.
Example 11
The alkali-free liquid accelerator prepared in this example was the same as in example 1 except that: the synergist is prepared by mixing acidic silica sol, sodium fluoride and ferrous sulfate, and the compounding ratio is 0.2:0.2: 1.
Comparative example 1
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: the composite material comprises 34% of polyaluminium sulfate, 16% of organic alcohol amine, 12% of synergist, 35% of modified suspension and 3% of pH regulator.
Comparative example 2
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: comprises 66 percent of polyaluminium sulfate, 5 percent of organic alcohol amine, 3 percent of synergistic agent, 21 percent of modified suspension and 5 percent of pH regulator.
Comparative example 3
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: in the preparation method of the modified suspension, the acidized sepiolite accounts for 10g, and the welan gum accounts for 3g, namely the weight ratio of the acidized sepiolite to the welan gum is 1: 0.3.
Comparative example 4
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: in the preparation method of the modified suspension, 10g of acidized sepiolite and 17g of welan gum are adopted, namely the weight ratio of the acidized sepiolite to the welan gum is 1: 1.7.
Comparative example 5
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: in the preparation method of the modified suspension, the amount of sodium persulfate is 0.12g, namely accounting for 0.3 percent of the total weight of the acidized sepiolite and the welan gum.
Comparative example 6
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: in the preparation method of the modified suspension, the amount of sodium persulfate is 0.68g, namely accounting for 1.7 percent of the total weight of the acidized sepiolite and the welan gum.
Comparative example 7
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: in the preparation method of the modified suspension, the dosage of the N, N' -methylene bisacrylamide is 0.16g, namely accounting for 0.4 percent of the total weight of the acidized sepiolite and the welan gum.
Comparative example 8
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: in the preparation method of the modified suspension, the dosage of the N, N' -methylene bisacrylamide is 0.6g, which is 1.5 percent of the total weight of the acidized sepiolite and the welan gum.
Comparative example 9
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: the synergist is prepared by mixing acidic silica sol, sodium fluoride and ferrous sulfate, and the compounding ratio is 0.2:0.04: 1.
Comparative example 10
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: the synergist is prepared by mixing acidic silica sol, sodium fluoride and ferrous sulfate, and the compounding ratio is 0.2:0.2: 1.
Comparative example 11
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: the synergist is prepared by mixing acidic silica sol and sodium fluoride, and the compounding ratio is 1: 0.5.
Comparative example 12
The alkali-free liquid accelerator prepared in this comparative example was the same as in example 1 except that: the synergist is prepared by mixing sodium fluoride and ferrous sulfate, and the compounding ratio is 0.5: 1.
Comparative example 13
The raw materials of the alkali-free liquid accelerator prepared by the comparative example are the same as those of the example 1 except that aluminum sulfate is selected and polyaluminum sulfate is not selected.
Comparative example 14
The same procedure as in example 1 was repeated except that the acidified sepiolite was replaced with the ordinary sepiolite as the starting material for the alkali-free accelerator prepared in this comparative example.
Comparative example 15
The alkali-free liquid accelerator of the present comparative example is different from example 1 only in that in the preparation method, step P2 is: adding all polyaluminium sulfate, adding the synergist after 15min, and stirring for reaction for 1.5-3 h.
Application example 1: performance test of alkali-free liquid accelerators prepared in examples 1 to 11 and comparative examples 1 to 15
The performance of the accelerating agent prepared in the examples 1-11 and the comparative examples 1-15 is tested, the test method is carried out according to GB/T35159-2017 accelerating agent for sprayed concrete, meanwhile, the stability of the accelerating agent after being respectively placed for 1, 3, 6 and 12 months is evaluated according to the 90d strength retention rate, and the test results are as follows:
TABLE 1 results of performance test of alkali-free liquid accelerators for examples 1 to 11 and comparative examples 1 to 15
Note: in the performance test of the above examples and comparative examples, the cement used is the reference cement P.I.42.5, the mixing amount of the accelerator is 5%, and the test temperature is 18-22 ℃.
As can be seen from the above Table 1, the accelerator composition provided by the present patent has higher stability and better compressive strength as seen from the comparative examples 1-3 and comparative examples 1 and 2. By comparing examples 1, 4-9 and comparative examples 3-8, the accelerating agent prepared by the modified suspension prepared by the special preparation method selected by the patent has higher stability and better compressive strength. By comparing examples 1, 10 and 11 and comparative examples 9 to 12, it can be seen that the kinds and proportions of the components of the synergist have a significant effect on the compressive strength and setting time of cement mortar prepared using the corresponding accelerator; only by adopting the proportion provided by the patent, better compressive strength and faster setting time can be achieved, obvious adverse effects can be generated on the compressive strength due to the lack of ferrous sulfate or acidic silica sol, and obvious adverse effects can be generated on the setting time due to the lack of ferrous sulfate or sodium fluoride; compared with common aluminum sulfate, the polyaluminum sulfate can ensure that the cement mortar has better quick setting effect and higher compressive strength. By comparing example 1 with comparative example 14, it can be seen that the replacement of the acidified sepiolite with the ordinary sepiolite significantly affects the stability of the accelerator prepared. As can be seen from the comparison of example 1 and comparative example 15, the stability of the accelerator is better when polyaluminium sulfate is added in two parts in sequence and stirred for reaction.
Claims (10)
1. An alkali-free liquid accelerator is characterized by comprising 40-62% of polyaluminium sulfate, 7-14% of organic alcohol amine, 5-10% of a synergist, 23-33% of a modified suspension and 3% of a pH regulator by weight;
the preparation method of the modified suspension comprises the following steps:
s1, stirring and dispersing the welan gum and water at the temperature of 45-55 ℃ for 0.5-1h according to the weight ratio of 1.5-3:100, adding a persulfate initiator, and keeping the temperature for 10-20min to obtain a mixed solution I;
s2, adding the acidized sepiolite and the cross-linking agent into water, and shearing at a high speed of 2000rpm at 1000 for 10-20min to obtain a mixed solution II, wherein the weight ratio of the total weight of the acidized sepiolite and the cross-linking agent to the water is 1: 10;
s3, dropwise adding the mixed solution II into the mixed solution I, and keeping the temperature at 50-65 ℃ for 0.5-1.5h after the dropwise adding is finished.
2. The alkali-free liquid accelerator according to claim 1, which comprises, by weight, 52% of polyaluminium sulfate, 10% of organic alcohol amine, 8% of synergist, 28% of modified suspension, and 2% of pH regulator.
3. The alkali-free liquid accelerator according to claim 1, wherein the weight ratio of the acidified sepiolite to the welan gum is 1: 0.5-1.5; the dosage of the persulfate initiator is 0.5 to 1.5 percent of the total weight of the acidized sepiolite and the rubber wheel; the cross-linking agent is at least one of organic compounds containing a plurality of unsaturated double bonds in the molecule, and the dosage of the cross-linking agent is 0.6-1.2 percent of the total weight of the acidized sepiolite and the rubber cement.
4. The alkali-free liquid accelerator according to claim 3, wherein the crosslinking agent is at least one of divinylbenzene, diisocyanate, and N, N-methylenebisacrylamide.
5. The alkali-free liquid accelerator according to claim 1, wherein the acidified sepiolite is prepared by the following method: adding sepiolite into 13-20% sulfuric acid at 50-75 deg.C, soaking for 12-24 hr, filtering, and oven drying.
6. The alkali-free liquid accelerator according to claim 5, wherein the weight ratio of sepiolite to sulfuric acid is 4 to 7: 100.
7. The alkali-free liquid accelerator as claimed in claim 1, wherein in step S3, the dropping time is 20-40 min.
8. The alkali-free liquid accelerator as claimed in claim 1, wherein the synergist is prepared by mixing acidic silica sol, sodium fluoride and ferrous sulfate, and the composite ratio is (0.2-1): 0.04-0.5): 1.
9. The alkali-free liquid accelerator according to claim 1, wherein the organic alcohol amine is at least one of diethanolamine, triethanolamine and triisopropanolamine; the pH regulator is at least one of phosphoric acid, tartaric acid, salicylic acid and citric acid.
10. A method for preparing the alkali-free liquid accelerator as set forth in any one of claims 1 to 8, comprising the steps of:
p1, adding organic alcohol amine into the modified suspension at 50-60 ℃ and stirring for 5-10min at the rotation speed of 130-250 rpm;
p2, adding half of the polyaluminium sulfate, continuously stirring for 10-15min, adding the synergist and the other half of the polyaluminium sulfate, and reacting for 1.5-3 h;
p3, adding a pH regulator, and stirring for 20-40min to obtain the finished product of the alkali-free liquid accelerator.
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