WO2024124734A1 - Inhibiteur composite d'agrégats alcalins et procédé de préparation associé - Google Patents
Inhibiteur composite d'agrégats alcalins et procédé de préparation associé Download PDFInfo
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- WO2024124734A1 WO2024124734A1 PCT/CN2023/083638 CN2023083638W WO2024124734A1 WO 2024124734 A1 WO2024124734 A1 WO 2024124734A1 CN 2023083638 W CN2023083638 W CN 2023083638W WO 2024124734 A1 WO2024124734 A1 WO 2024124734A1
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- WIPO (PCT)
- Prior art keywords
- alkali
- composite inhibitor
- aggregate composite
- polyethylene glycol
- organic acid
- Prior art date
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000003112 inhibitor Substances 0.000 title claims abstract description 41
- 239000003513 alkali Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 42
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 42
- 150000007524 organic acids Chemical class 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010457 zeolite Substances 0.000 claims abstract description 25
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000012024 dehydrating agents Substances 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011964 heteropoly acid Substances 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 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 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229940095564 anhydrous calcium sulfate Drugs 0.000 claims description 3
- 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 3
- -1 diisopropyl titanate Chemical compound 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- COPFMLHTUMFXGR-OSZYEJKESA-N (Z)-19-methyl-1-[(Z)-octadec-9-enoxy]icos-9-ene Chemical group C(C)(C)CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC COPFMLHTUMFXGR-OSZYEJKESA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 239000004567 concrete Substances 0.000 abstract description 30
- 238000005336 cracking Methods 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- 239000004568 cement Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000004576 sand Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229940095672 calcium sulfate Drugs 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000009191 jumping Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 1
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003823 mortar mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011178 precast concrete Substances 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000002699 waste material 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
- C04B40/0042—Powdery mixtures
-
- 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
Definitions
- the present disclosure relates to the field of concrete building materials, and in particular to an alkali-aggregate composite inhibitor.
- the present disclosure also relates to a preparation method of the alkali-aggregate composite inhibitor.
- Concrete has become the world's largest building material due to its excellent cost-effectiveness.
- Concrete is a composite material obtained by mixing and hardening cementitious materials, coarse and fine aggregates and water.
- the main type of cementitious materials is cement. Cement undergoes a hydration reaction when it comes into contact with water, bonding coarse and fine aggregates together. Since the international energy crisis in the 1970s, the cement industry has gradually changed from wet production to dry production, which has increased the alkali content of cement.
- Alkali-aggregate reaction is the slow reaction between the alkali in cement and the active silica in aggregate to form silicate gel.
- the silicate gel accumulates over a long period of time and its output increases. It has strong water absorption, causing the silicate gel to expand in volume, thereby inducing expansion stress from the inside to the outside of the concrete structure, causing concrete cracking, reducing the mechanical properties of concrete, and damaging the durability of concrete.
- Alkali-aggregate reaction cracking has been found. Some urban highway traffic has cracks in its moist parts a few years after construction and sampling has confirmed that it is alkali-aggregate reaction.
- the present disclosure proposes an alkali-aggregate composite inhibitor to inhibit the alkali-aggregate reaction of concrete.
- An alkali aggregate composite inhibitor the raw materials for preparing the alkali aggregate composite inhibitor include the following components by weight: 0.5-2.0 parts of a titanate coupling agent, 15-30 parts of an ester of polyethylene glycol and an organic acid, and 200-260 parts of a medium-pore zeolite.
- the titanate coupling agent includes di(triethanolamine)titanate diisopropyl ester, bis(di At least one of a chelate of octyl pyrophosphate) ethylene titanate and triolamine, isopropyl tri(dioctyl phosphate) titanate, and isopropyl dioleyloxy(dioctyl phosphate) titanate.
- the molar ratio of the alcohol acid in the ester of polyethylene glycol and organic acid is (5-8): (12-18).
- the weight average molecular weight of the polyethylene glycol is 200-600.
- the organic acid is at least one of formic acid, acetic acid and propionic acid.
- the medium pore zeolite includes at least one of ferrierite, Y-type zeolite and ZSM-5 zeolite.
- the present disclosure also provides a method for preparing an alkali-aggregate composite inhibitor, the method comprising the following steps:
- the preparation method of the ester of polyethylene glycol and organic acid comprises the following steps:
- the catalyst is at least one of phosphotungstic heteropoly acid, SO 4 2- /SiO 2 -TiO 2 , cerium sulfate and zirconium sulfate.
- the dehydrating agent is at least one of calcium oxide and anhydrous calcium sulfate.
- the preparation of the ester of polyethylene glycol and organic acid is carried out by heating in an oil bath.
- the amount of the catalyst is 0.1-0.3% of the amount of the reactants.
- An alkali aggregate composite inhibitor the raw materials for preparing the alkali aggregate composite inhibitor include the following components by weight: 0.5-2.0 parts of a titanate coupling agent, 15-30 parts of an ester of polyethylene glycol and an organic acid, and 200-260 parts of a medium-pore zeolite.
- the alkali-aggregate composite inhibitor disclosed in the present invention is composed of three main components: titanate coupling agent, esterification product of polyethylene glycol and organic acid, and medium-porous zeolite powder.
- the medium-porous zeolite powder can rely on its own porous structure to produce adsorption effect on titanate coupling agent and esterification product of polyethylene glycol and organic acid, so that the adsorbed titanate coupling agent and esterification product of polyethylene glycol and organic acid are slowly released in the hardened concrete system to play a long-term effect.
- the long carbon chain hydrophobic group of the titanate coupling agent is grafted onto the surface of the aggregate, which can hydrophobically modify the active silica on the surface of the aggregate, so that the silica on the surface of the aggregate has a hydrophobic effect, so that water cannot adhere to the surface of the aggregate, reducing the wetting effect of water molecules on the active silica in the hardened concrete under a humid environment, and alkaline substances cannot be ionized by water to produce hydroxide ions, which is helpful to inhibit the reaction between alkaline ions and active silica in the hardened concrete.
- the titanium element contained in the titanate coupling agent can improve the durability of concrete, and an appropriate amount of titanium dioxide helps to improve the self-cleaning performance of concrete.
- the titanate coupling agent may preferably be at least one of diisopropyl di(triethanolamine)titanate, a chelate of bis(dioctyl pyrophosphate)ethylene titanate and triolamine, isopropyl tri(dioctyl phosphate acyloxy) titanate, and isopropyl dioleyloxy(dioctyl phosphate acyloxy) titanate.
- the ester of polyethylene glycol and organic acid undergoes hydrolysis reaction under alkaline conditions to generate organic acid, which neutralizes the alkali in the system, reduces the pH value of hardened concrete, and inhibits alkali-aggregate reaction.
- the molar ratio of the alcohol acid in the ester of polyethylene glycol and organic acid is (5-8): (12-18).
- the weight average molecular weight of the polyethylene glycol is 200-600. The molecular weight in this range is relatively small, the esterification efficiency is high, and more organic acid can be released by hydrolysis.
- the organic acid can preferably be at least one of formic acid, acetic acid and propionic acid. This organic acid has a strong acidity and is more efficient in neutralization with alkali.
- the present disclosure also provides a method for preparing an alkali-aggregate composite inhibitor, the method comprising the following steps:
- 0.5-0.8 mol of polyethylene glycol is added to the reactor, the oil bath heater is turned on, the temperature is set to 60-65°C, stirring is turned on, 1.2-1.8 mol of organic acid monomer and catalyst are added, and after reacting for 2-3 hours, a dehydrating agent is added, and the reaction is continued for 2-3 hours. The dehydrating agent is continued to be added, and the reaction is cooled to room temperature to obtain a viscous paste of polyethylene glycol and organic acid ester.
- the amount of catalyst used in this step is 0.1-0.3% of the mass of the reactants, and it can be preferably at least one of phosphotungstic heteropoly acid, SO 4 2- /SiO 2 -TiO 2 , cerium sulfate and zirconium sulfate, which has a high catalytic efficiency compared to ordinary concentrated sulfuric acid.
- the total amount of the dehydrating agent is 0.5-1.0 mol, and it can be preferably at least one of calcium oxide and anhydrous calcium sulfate. The catalyst and the dehydrating agent do not need to be removed separately.
- the preparation method of the ester of polyethylene glycol and an organic acid includes the following process steps: first, 0.8 mol of polyethylene glycol with a weight average molecular weight of 200 is added into a reactor, the oil bath heater is turned on, the temperature is set to 62° C., stirring is turned on, 1.8 mol of formic acid and 0.36 g of zirconium sulfate are added, and after reacting for 3 hours, 28 g of calcium oxide is added, the reaction is continued for 3 hours, 28 g of calcium oxide is added, and the mixture is cooled to room temperature to obtain a viscous paste, that is, the ester of polyethylene glycol and an organic acid is obtained.
- alkali aggregate composite inhibitor Add 210g of medium-pore Y-type zeolite powder to a kneader, heat to 62°C, add 16g of ester of polyethylene glycol and organic acid, knead for 1.2 hours, then add 1.0g of isopropyl tri(dioctylphosphoyloxy) titanate, knead for 1.5 hours, cool to room temperature, and obtain powdery Alkali aggregate composite inhibitor.
- the preparation method of the ester of polyethylene glycol and an organic acid comprises the following process steps: firstly, 0.6 mol of polyethylene glycol with a weight average molecular weight of 400 is added into a reactor, the oil bath heater is turned on, the temperature is set to 65° C., stirring is turned on, 1.4 mol of acetic acid and 0.32 g of phosphotungstic heteropoly acid are added, and after reacting for 2 hours, 35 g of calcium sulfate is added, and reacting for 3 hours, 35 g of calcium sulfate is continuously added, and the mixture is cooled to room temperature to obtain a viscous paste, that is, the ester of polyethylene glycol and an organic acid is obtained.
- alkali-aggregate composite inhibitor Add 260g of medium-pore ferrous alkali zeolite powder into a kneader, heat to 62°C, add 30g of ester of polyethylene glycol and organic acid, knead for 1.5 hours, then add 2.0g of chelate of bis(dioctyloxypyrophosphate)ethylene titanate and triolamine, knead for 2 hours, cool to room temperature, and obtain a powdery alkali-aggregate composite inhibitor.
- the preparation method of the esterification product of polyethylene glycol and organic acid includes the following process steps: first, 0.5 mol of polyethylene glycol with a weight average molecular weight of 600 is added into a reactor, the oil bath heater is turned on, the temperature is set to 65°C, stirring is turned on, 0.6 mol of formic acid and 0.2 g of SO42- / SiO2 - TiO2 catalyst are added, after reacting for 2.5 hours, 30 g of calcium oxide are added, 0.6 mol of acetic acid and 0.18 g of SO42- / SiO2 - TiO2 catalyst are added, the reaction is continued for 2.5 hours, 30 g of calcium oxide are added, and the reaction is cooled to room temperature to obtain a viscous paste, that is, the esterification product of polyethylene glycol and organic acid is obtained.
- the preparation method of the alkali-aggregate composite inhibitor is as follows: 230 g of ZSM-5 medium-pore zeolite powder is added to a kneader, heated to 60° C., 25 g of an ester of polyethylene glycol and an organic acid is added, kneaded for 1.5 hours, and then 2 g of a chelate of bis(dioctyloxypyrophosphate)ethylene titanate and triolamine is added, kneaded for 1.5 hours, and cooled to room temperature to obtain a powdery alkali-aggregate composite inhibitor.
- the method for preparing the ester of polyethylene glycol and organic acid comprises the following process steps: firstly, 0.4 mol of polyethylene glycol with weight average molecular weight of 200 and 400 respectively is added into the reactor, the oil bath heater is turned on, the temperature is set to 63°C, stirring is turned on, 1.8 mol of propionic acid and 0.3 g of SO42- / SiO2 - TiO2 catalyst are added, after reacting for 3 hours, 36 g of calcium sulfate is added, and 0.2 g of SO42-/SiO2-TiO2 catalyst is added , and the reaction is continued for 3 hours. When the mixture was stirred for 2 hours, 36 g of calcium sulfate was added and the mixture was cooled to room temperature to obtain a viscous paste, that is, an ester of polyethylene glycol and an organic acid.
- Preparation of alkali-aggregate composite inhibitor Add 260 g of ZSM-5 zeolite medium-pore zeolite powder into a kneader, heat to 65°C, add 20 g of an ester of polyethylene glycol and an organic acid, knead for 1.5 hours, then add 1 g each of a chelate of bis(dioctylpyrophosphate)ethylene titanate and triolamine and isopropyl tri(dioctylphosphoacyl) titanate, knead for 1.8 hours, cool to room temperature, and obtain a powdery mixture.
- Examples 1-4 were used for alkali-aggregate reaction test. Before the test, petrographic analysis of the machine-made sand in the stockpile showed that it was granite, and the active mineral contained was strained quartz with a content of about 38%. According to GB/T14684-2011, the samples of Examples 1-4 were used for alkali-aggregate reaction test, the cement used was Esheng PO.42.5 ordinary Portland cement, and the fly ash used was primary ash. First, the sand was graded and sieved with a square hole sieve to remove sand with a particle size greater than 4.75 mm and less than 0.15 mm. The mass of each particle size of sand used in the alkali-aggregate reaction experiment is shown in Table 1:
- the mortar mixing should be carried out according to the provisions of GB/T 17671. After the mixing is completed, the mortar is immediately loaded into the test mold equipped with the expansion probe in two times, and each layer is tamped 40 times. Note that the expansion probe should be carefully tamped around. After pouring, use a steamed knife to scrape off the excess mortar, smooth it, number it and indicate the measurement direction. Each group of tests is formed into 3 groups.
- test results are shown in Table 2:
- the test block showed brittleness after 180 days, and its expansion rate reached 0.5%, and the expansion rate after 14 days was 0.12%, which was much higher than the requirement of less than 0.1% in GB14684-2011 for an expansion rate of less than 0.1% after 180 days, indicating that its alkali-aggregate reaction was very serious.
- 1st-grade fly ash was used to replace 30% of cement. In the first 30 days, the expansion rate of the test block was less than 0.1%, but the expansion rate of the test block after 60 days reached 0.1%, and the expansion rate of the test block after 180 days reached 0.18%, indicating that fly ash reduced the alkali-aggregate reaction to a certain extent, but still could not meet the standard requirements.
- the alkali-aggregate composite inhibitor provided by the present disclosure has the advantages of low dosage and good inhibition effect, which plays an energy-saving and efficiency-enhancing role in construction projects.
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- Ceramic Engineering (AREA)
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- Curing Cements, Concrete, And Artificial Stone (AREA)
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Abstract
La présente divulgation concerne un inhibiteur composite d'agrégats alcalins, ainsi qu'un procédé de préparation associé. Les matières premières de préparation de l'inhibiteur composite d'agrégats alcalins comprennent les composants suivants, en parties en poids : de 0,5 à 2,0 parties d'un agent de couplage au titanate, de 15 à 30 parties d'un produit estérifié de polyéthylène glycol et d'un acide organique et de 200 à 260 parties d'une zéolite mésoporeuse. L'inhibiteur composite d'agrégats alcalins est avantageux pour inhiber une réaction d'agrégats alcalins du béton à un stade ultérieur, réduisant ainsi le risque de fissuration du béton à un stade ultérieur, améliorant la durabilité de l'ingénierie et des bâtiments en béton, et réduisant les coûts d'entretien ultérieurs des projets d'ingénierie.
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JP2007169144A (ja) * | 2005-11-04 | 2007-07-05 | Tokuyama Corp | アルカリ性低減剤 |
JP2008247686A (ja) * | 2007-03-30 | 2008-10-16 | Taiheiyo Cement Corp | アルカリ骨材反応抑制剤 |
JP2010024112A (ja) * | 2008-07-23 | 2010-02-04 | Denki Kagaku Kogyo Kk | セメント混和材及びセメント組成物 |
JP2022134233A (ja) * | 2021-03-03 | 2022-09-15 | Ube三菱セメント株式会社 | セメント組成物及びその製造方法、アルカリシリカ反応抑制剤、アルカリシリカ反応抑制方法 |
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JP2008247686A (ja) * | 2007-03-30 | 2008-10-16 | Taiheiyo Cement Corp | アルカリ骨材反応抑制剤 |
JP2010024112A (ja) * | 2008-07-23 | 2010-02-04 | Denki Kagaku Kogyo Kk | セメント混和材及びセメント組成物 |
JP2022134233A (ja) * | 2021-03-03 | 2022-09-15 | Ube三菱セメント株式会社 | セメント組成物及びその製造方法、アルカリシリカ反応抑制剤、アルカリシリカ反応抑制方法 |
CN115611551A (zh) * | 2022-12-16 | 2023-01-17 | 石家庄市长安育才建材有限公司 | 碱骨料复合抑制剂及其制备方法 |
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