CN112919832A - Modified grinding-aid early strength agent for steel slag and preparation method and application method thereof - Google Patents
Modified grinding-aid early strength agent for steel slag and preparation method and application method thereof Download PDFInfo
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- CN112919832A CN112919832A CN202110355920.5A CN202110355920A CN112919832A CN 112919832 A CN112919832 A CN 112919832A CN 202110355920 A CN202110355920 A CN 202110355920A CN 112919832 A CN112919832 A CN 112919832A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 81
- 239000010959 steel Substances 0.000 title claims abstract description 81
- 239000002893 slag Substances 0.000 title claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 86
- -1 ester compounds Chemical class 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 12
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000007792 addition Methods 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043276 diisopropanolamine Drugs 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 27
- 230000008569 process Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
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- 239000000047 product Substances 0.000 description 15
- 238000006703 hydration reaction Methods 0.000 description 13
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- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
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- 229910014472 Ca—O Inorganic materials 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229940043237 diethanolamine Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- ZSFDBVJMDCMTBM-UHFFFAOYSA-N ethane-1,2-diamine;phosphoric acid Chemical compound NCCN.OP(O)(O)=O ZSFDBVJMDCMTBM-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- WZXYIWMZCIFNRB-UHFFFAOYSA-N 2-methylprop-2-enoate;tris(2-hydroxyethyl)azanium Chemical compound CC(=C)C(O)=O.OCCN(CCO)CCO WZXYIWMZCIFNRB-UHFFFAOYSA-N 0.000 description 1
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 description 1
- PZBWHCLIJWJZKA-UHFFFAOYSA-N C(C(C)O)O.C(C)O.C(C)O Chemical compound C(C(C)O)O.C(C)O.C(C)O PZBWHCLIJWJZKA-UHFFFAOYSA-N 0.000 description 1
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007547 defect Effects 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
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- 230000009977 dual effect Effects 0.000 description 1
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- 229910052840 fayalite Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000006911 nucleation Effects 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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Images
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
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
Abstract
The invention discloses a modified grinding-assisted early strength agent for steel slag, a preparation method and an application method thereof, and relates to the field of steel slag grinding. The modified early strength grinding aid comprises (a) 60-75% of ester compounds by the total weight of the modified early strength grinding aid, (b) 5-15% of polyacrylic acid by the total weight of the modified early strength grinding aid, and (c) 10-35% of alcohol amine and acrylic acid monomers by the total weight of the modified early strength grinding aid; the preparation method comprises the steps of adding water into alcohol amine and acrylic acid, uniformly mixing, heating while stirring, reacting for 3-4 hours at 60-80 ℃, cooling the solution to room temperature to obtain the modified grinding-assisted early strength agent, and applying the modified grinding-assisted early strength agent to grinding of a gel material with high steel slag content, so that the problems of low grinding efficiency, low activity of the steel slag in the early stage, complex synthesis process, high cost and the like of the conventional grinding aid are solved. The invention has the advantages of simple preparation process, low raw material cost, stable finished product quality, stable performance and good use effect, and the 7d strength is increased by more than or equal to 30 percent.
Description
Technical Field
The invention relates to steel slag grinding aid, in particular to a modified grinding-aid early strength agent for steel slag, a preparation method and an application method thereof.
Background
The steel slag is a necessary byproduct in the steel industry, and the discharge amount accounts for about 15-20% of the yield of the crude steel. A large amount of steel slag is not effectively utilized, which causes harm to the environment and occupies a large amount of land.
The steel slag is a potentially active cementing material, has similar chemical composition to cement clinker, but contains a large amount of unstable free CaO, FeO and MgO, and the main mineral composition of the steel slag is C2S (dicalcium silicate), C3S (tricalcium silicate), RO phase, magnesian rosepside, small amount of glass phase, fayalite, and C3A (tricalcium aluminate), f-CaO and steel grains with different quantities. In order to largely consume the steel slag and fully utilize the gelling property of the steel slag, the steel slag is used for producing building materials and is a main mode for treating the steel slag, but because the steel slag has better toughness and higher content of simple substance iron and sandstone particles, the grinding is difficult and the gelling activity is difficult to excite.
In order to solve the problem, domestic and foreign enterprises generally use an early strength agent and a grinding aid which take triethanolamine as a raw material, and the early strength agent and the grinding aid can reduce the phenomenon of electrostatic adsorption and ball wrapping in the steel slag grinding process, increase the steric hindrance between particles, prevent the secondary aggregation of ultrafine particles, improve the fluidity of the steel slag, improve the grinding effect and reduce the energy consumption. But the raw material price is higher, the triethanolamine has volatility, the high-temperature environment can cause volatilization waste during grinding, the grinding cost is increased, and the triethanolamine grinding aid has a better effect on the early strength but has insignificant increase of the later strength.
Therefore, many scholars have made corresponding researches on the steel slag grinding aid and the early strength agent and have achieved certain results.
Chinese patent with application number 200510047822.6 discloses a multifunctional cement grinding aid, which is a mixture of fly ash, sodium chloride, triethanolamine, sodium silicate, gypsum, sodium benzoate, zinc ore powder and diethylene glycol, and the weight ratio of each component is as follows: 10-60% of fly ash, 15-55% of sodium chloride, 5-35% of triethanolamine, 0.05-10% of sodium silicate, 0.5-6% of gypsum, 0.2-8% of sodium benzoate, 0.3-12% of zinc ore powder and 0.3-5% of diethylene glycol. The grinding aid has complex components and high cost, and is developed aiming at fine grinding of cement. Because the steel slag has different components from cement, the improvement effect on the activity index of the steel slag is not obvious.
The application No. 201410124868.2 Chinese patent discloses a steel slag grinding aid and a preparation method thereof, wherein the steel slag grinding aid comprises 8-12 parts by weight of acrylamide, 8-12 parts by weight of benzamide, 15-20 parts by weight of alkanolamine, 5-10 parts by weight of ethylenediamine phosphate, 10-15 parts by weight of calcium lignosulfonate, 8-12 parts by weight of sodium lignosulfonate, 0.1-0.5 part by weight of tributyl phosphate and 20-80 parts by weight of water. During preparation, acrylamide, benzamide and alkanolamine are added into water according to a certain proportion to be dissolved, then ethylenediamine phosphate, calcium lignosulfonate and sodium lignosulfonate are sequentially added, mixed and stirred, tributyl phosphate is added, and the mixture is stirred to obtain the steel slag grinding aid. The grinding aid is simple in preparation method, but the raw materials of the grinding aid are more in variety, so that the grinding aid is not beneficial to on-site preparation.
Chinese patent application No. 201610911194.X discloses a high molecular grinding aid and a preparation method thereof. In the patent, triethanolamine, polyether monomers and other substances are compounded to prepare the grinding aid, and toluene with water and NaOH are added to adjust ph in the preparation process. The method has the disadvantages of complex preparation process and high cost; toluene is toxic and is not suitable for on-site preparation.
The Chinese patent with the application number of 201510701487.0 discloses a steel slag cement grinding aid and a preparation method thereof, but water glass is easy to precipitate with other components of the grinding aid; the Chinese patent of application No. 201410013243.9 discloses a slag and steel slag grinding-aid activator, wherein anhydrous sodium sulphate is easy to separate out at low temperature. The two schemes can generate precipitation in the production process to reduce the effect of the medicament and influence the quality stability.
The Chinese patent application No. 201810330508.6 discloses a liquid grinding aid for improving the grinding efficiency of steel slag. The scheme only provides assistance for grinding aid, and does not help the improvement effect of the activity index of the steel slag.
The study "synthesis of triethanolamine compounds with different structures and grinding aid effect thereof on cement" (Chinese powder technology, 2011, 06: 63-67, Yuanyongtao, etc.) synthesizes a triethanolamine methacrylate grinding aid by using methacrylic acid and triethanolamine. The preparation method is carried out under the high-temperature condition, increases the energy consumption and has high cost.
Through retrieval, Yuanyuan of Jinan university discloses a paper named 'modification and application research of triethanolamine cement grinding aid' at 2012, 5.1.A, the paper aims at esterification and ammonification modification of triethanolamine to ensure that the triethanolamine has better grinding aid enhancing effect under the same grinding process and addition amount, and selects excellent modified triethanolamine to compound a composite cement grinding aid, so as to systematically research the performance of the composite cement grinding aid and develop a novel efficient composite cement grinding aid of the modified triethanolamine, wherein the novel efficient composite cement grinding aid comprises alpha-methylacrylic acid esterification modification of the triethanolamine. Because the ratio of clinker minerals in the cement is far greater than that of steel slag, and f-CaO is not contained, the necessity of activity excitation is relatively low, the requirements on medicaments mainly include grinding aid, and the requirement on the early strength function is not obvious. The grinding aid is obviously different from the dual functional requirement of steel slag utilization on grinding aid-early strength of the medicament. Therefore, the cement grinding aid theory cannot be simply applied to steel slag utilization.
The Chinese patent application No. 201610392181.6, application publication No. 2016, 10, month 26 and discloses an alcamines early strength agent, and a preparation method and application thereof. The early strength agent disclosed by the patent is mainly prepared by reacting diethanol monopropylene glycol amine with diethanol amine and epoxy propanol in a solvent, is simple in preparation method and mild in condition, and does not need separation treatment. The obtained early strength agent has excellent early strength performance, and has good adaptability with a polycarboxylic acid water reducing agent and an inorganic salt early strength agent, and the early strength performance is superior to the common alcohol amine early strength agents such as triethanolamine, diethanol monoisopropanolamine and the like. However, the early strength agent of the patent has poor grinding-aiding function due to low molecular weight; has early strength function, is mainly used for preparing concrete and is difficult to be used in steel slag utilization.
Therefore, aiming at the utilization of steel slag, the research and development of the grinding aid which has low cost, simple preparation process, on-site preparation and good grinding-aiding early-strengthening effect is particularly important.
Disclosure of Invention
1. Problems to be solved
Aiming at the defects of the prior art, the invention takes the alcohol amine as the main raw material to modify the alcohol amine, and aims to provide the additive which has low cost and simple preparation process, can be prepared and used on site and integrates grinding aid and early strength.
The invention also provides a preparation method of the modified grinding-assisted early strength agent for steel slag, and aims to prepare the modified grinding-assisted early strength agent more suitable for steel slag grinding under mild conditions.
The invention also provides an application method of the modified grinding-aid early strength agent for the steel slag, which aims to control the using amount of the modified grinding-aid early strength agent to be applied to the grinding of a cementing material containing more than 50% of the steel slag, so that the steel slag can be more fully utilized.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a modified grinding-aid early strength agent for steel slag comprises (a) 60-75% of ester compounds by the total weight of the modified grinding-aid early strength agent, (b) 5-15% of polyacrylic acid by the total weight of the modified grinding-aid early strength agent, and (c) 10-35% of alcohol amine and acrylic acid monomers by the total weight of the modified grinding-aid early strength agent, wherein the mass of the alcohol amine monomer is 10-30% of the total weight of the modified grinding-aid early strength agent, and the mass of the acrylic acid monomer is 0-5% of the total weight of the modified grinding-aid early strength agent.
Further, the ester compound is an alcohol amine and an acrylic acid esterification product.
The preparation method of the modified grinding-aid early strength agent for the steel slag comprises the steps of adding water into alcohol amine and acrylic acid, uniformly mixing, heating while stirring, reacting for 3-4 hours at the temperature of 60-80 ℃, and cooling the solution to room temperature to obtain the modified grinding-aid early strength agent.
Further, the alcohol amine, the acrylic acid and the water are respectively in parts by weight:
35-55 parts of alcohol amine;
40-50 parts of acrylic acid;
50-120 parts of water.
Further, the alcohol amine is any one alcohol compound of diethanolamine, triethanolamine, dipropanol amine, tripropanol amine, diisopropanol amine, triisopropanol amine and dibutanol amine.
Further, when the raw materials are placed in a round-bottom flask for reaction, in order to facilitate stirring, the mixture is stirred uniformly by a magnetic stirrer, a condensation reflux device is added, after reaction for 3-4 hours, heating is stopped, stirring is continued, and the modified grinding-aid early strength agent is obtained after the solution is cooled to room temperature.
Furthermore, the rotating speed of stirring is 350 r/min-550 r/min.
The application method of the modified grinding-aid early strength agent for the steel slag comprises the steps of diluting the modified grinding-aid early strength agent with water, uniformly spraying or dropwise adding the diluted modified grinding-aid early strength agent on the surface of a raw material, wherein the dosage of the diluted modified grinding-aid early strength agent is 0.01-0.07 percent of the weight of a ground cementing material.
Furthermore, in the cementing material, the addition amount of the steel slag is more than 50 percent of the total weight of the cementing material.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the modified grinding-aid early strength agent is applied to grinding of steel slag, the steel slag is different from a cement material, and clinker components are far smaller than that of the cement, so that the existing research finds that the grinding-aid early strength agent has the best grinding-aid early strength effect when more esters are in the grinding-aid early strength agent aiming at the cement material; the modified grinding-aid early strength agent is provided for grinding steel slag, and the inventor finds for the first time that the utilization rate of the steel slag is higher by matching the synergistic effect of polyacrylic acid, alcohol amine and acrylic acid monomers under the condition that the more ester compounds are better and the ester compounds account for 60-75% of the weight of the steel slag in grinding;
(2) the ester compound formed by the reaction in the modified grinding-aid early strength agent changes the original bond length and bond type of the alcohol amine compound, so that more polar molecules can be adsorbed on the surface of particles by a monomolecular layer or a polymolecular layer, the surface energy of the particles is reduced, and the tendency of agglomeration of the particles due to mutual attraction is weakened; the ester compound adsorbed on the surface of the particles forms a layer of film on the surface of the particles, so that the flowability of the particles is improved, the crushing force of the particles in the grinding process is more uniform, the particle size distribution of the particles is more concentrated, the phenomena of over-coarse and over-grinding of the particles are prevented, the content of the particles with the key effect on the strength of 3-32 mu m is increased, and the grinding energy consumption can be saved; in addition, the ester compounds adsorbed on the surfaces of the particles can enable original cracks to continue to develop and enable large particles to be broken, so that a grinding aid effect is achieved;
the more polar groups of the molecule, the stronger the polarity of the groups, and the better the early strength effect of the medicament. The ester bond of polar group is introduced into the generated ester, the structure and the property of the alcamines are changed, and the C in the cementing material can be promoted3A、C3S hydration promotes the generation of C-A-H, accelerates the growth of C-S-H gel and C-A-S-H gel, increases the yield of AFt, improves the gridding degree of a system, and accelerates the hydration reaction speed. Unsaturated hydrocarbon bonds in the esterified compounds change the balance structure of molecules of the alcohol amine compounds, so that an unshared pair of electrons on N atoms in the molecules of the alcohol amine compounds can more easily form covalent bonds with metal cations to generate more stable chelates, the chelates can form a plurality of soluble regions in a solution, the diffusion rate of hydration products is improved, and the particle surface C at the initial stage of hydration is caused to be3The hydrate layer of A is destroyed, and C is further increased3The dissolution rate of A is increased, thereby accelerating the dissolution of A and CaSO4After reaction, AFt is rapidly generated. Ca in the system2+、Al3+The concentration is reduced, which in turn promotes C3S、C2S hydration reaction is carried out to generate more C-S-H gel, so that the system is more compact, and the hydration reaction speed is accelerated;
the generated esterified substance also has an emulsifying effect, is doped into a steel slag composite cementing material system, is adsorbed on the surface of material particles to form a layer of charged hydrophilic film, so that the surface tension of slurry is reduced, the infiltration and permeation of water molecules on the particles are enhanced, the particles are more fully contacted with the water molecules, the volume expansion of a solid phase body caused by hydration is enhanced, a coking layer of the particles is continuously peeled off, the hydrolysis of the particles is promoted, and the hydration reaction is accelerated;
in addition, the alcamines monomer also has stronger early strength function; the formed polycarboxylic acid also has good water reducing effect, and the strength of a sample after the steel slag is hydrated can be obviously improved. Therefore, under the synergistic effect of the above-mentioned several factors, the early-strengthening effect can be strengthened. The technology realizes the preparation of the grinding aid and early strength agent suitable for the utilization of the steel slag under the conditions of simple process and no pursuit of high yield of esterification products;
(3) the modified grinding-aid early strength agent is mainly used for grinding steel slag, and active minerals can be dissociated only by grinding aid due to high hardness of the steel slag, so that the mechanical excitation efficiency is improved; the invention utilizes the existence of f-CaO in the steel slag to accelerate the hydration reaction speed, so that the f-CaO forms a hydration product with gelling activity as soon as possible, and the harm of the volume instability of the f-CaO is eliminated; therefore, aiming at the utilization of the steel slag, an excitant with double functions of grinding aid and early strength must be developed;
in the steel slag, Si-O covalent bonds and Ca-O ionic bonds mainly exist, the Ca-O ionic bonds are preferentially broken in the grinding process, and after the Ca-O bonds are broken, Ca on two sides of the broken bonds is generated due to the generation of electron density difference2+And O2-The active points are formed, so that the cross sections have the tendency of mutual attraction or are polymerized into new large particles; the ester compound provides external ions and molecules, and the ions and molecules are adsorbed on the cross section to meet unsaturated electrovalence bonds, so that the aggregation tendency of particles is weakened, and the cross section is prevented from polymerizing again; after the agglomeration is eliminated, the mechanical work can better act on single particles, thereby improving the grinding efficiency; in addition, the formed polyacrylic acid, the alcohol amine monomer and the acrylic acid monomer also have good grinding-aid effect and have synergistic effect with each other; therefore, although the temperature is lower and no catalyst is added, the yield of the ester compound formed by the reaction is slightly lower, but the overall grinding-aid effect is still better;
(4) the preparation method has lower esterification reaction temperature and lower esterification product yield, but practices find that unexpected effects are generated, namely other products, such as polyacrylic acid and alcohol amine monomers can still play the roles of grinding aid and early strength, and generate synergistic effect with the esterification products, and the polyacrylic acid also has water reducing effect and has stronger pertinence to the utilization of the steel slag;
(5) compared with other technologies, the preparation method has the advantages that the preparation process is simple, the cost is low, and the double effects of grinding aid and early strength are achieved; the reagent is used as a modifying reagent of alcohol amine, can be adsorbed on the surface of steel slag particles, further permeates into the micro-particles of solid particles, enlarges cracks and strengthens the micronization process of the steel slag; the grinding aid also spontaneously generates physical and chemical adsorption on the steel slag, so that the surface energy of steel slag particles is effectively reduced; meanwhile, steel slag particles are wrapped into a film, so that secondary agglomeration of fine particles is prevented, the flowability and the dispersibility of the steel slag micro powder in a mill are improved, and the grinding efficiency is obviously improved; hydroxyl and carboxyl in the grinding-aid early strength agent can form a coordination compound with a hydration product, and the coordination compound is uniformly sprayed on the surface of a raw material during grinding, so that the steric hindrance among particles is increased, the nucleation process of a micro-acceleration hydration product is changed, and the early strength and the later strength are improved; the potential among the particles prevents the particles from reuniting again, thereby reducing the grinding energy consumption; the modifier can promote grinding, can form a chelate with iron element, promotes hydration and increases early strength.
Drawings
FIG. 1 is a flow chart of a preparation process of the modified grinding-aid early strength agent of the invention;
FIG. 2 is a FT-IR plot of the modified grinding aid early strength agent of example 1.
Detailed Description
The invention is further described with reference to specific examples.
Table 1 shows the raw material formulas for preparing the modified grinding-assisted early strength agent in examples 1-5.
Table 1 raw material formulations in the examples
Example 1
A modified grinding-assisted early strength agent using steel slag comprises the following raw materials in parts by weight:
50 parts of triethanolamine;
50 parts of acrylic acid;
100 parts of water;
the preparation method is shown as a flow chart in figure 1 and comprises the following steps:
(1) weighing the raw materials according to the proportion, and putting the raw materials into a round-bottom flask to be uniformly mixed;
(2) putting the round-bottom flask into a magnetic stirrer, wherein the rotating speed is 500r/min, the temperature is 70 ℃, adding a condensation reflux device, and reacting for 3.5 hours;
(3) stopping heating, continuing stirring, and cooling the solution to room temperature to obtain the modified grinding-aid early strength agent.
The modified grinding-aid early strength agent of the embodiment is detected by infrared as shown in figure 2, wherein 3628cm-1Is located at 3363cm and is an O-H absorption peak-1Is shown as an N-H absorption peak at 1734cm-1Is represented by C ═ O absorption peak, 1221cm-1The position is a C-O-C telescopic absorption peak. The content of various substances is measured by adopting a liquid chromatography, and the modified grinding-aid early strength agent organic matter of the embodiment is calculated to have the mass ratio of the ester compound of 71.3 percent, the mass ratio of the polyacrylic acid of 13.4 percent, the mass ratio of the alcohol amine monomer of 12.8 percent and the mass ratio of the acrylic acid monomer of 2.5 percent.
Example 2
A modified grinding-assisted early strength agent using steel slag is characterized by comprising the following raw materials in parts by weight:
45 parts of triisopropanolamine;
55 parts of acrylic acid;
90 parts of water;
the preparation method is shown as a flow chart in figure 1 and comprises the following steps:
(1) weighing the raw materials according to the proportion, and putting the raw materials into a round-bottom flask to be uniformly mixed;
(2) putting the round-bottom flask into a magnetic stirrer, wherein the rotating speed is 400r/min, the temperature is 60 ℃, adding a condensation reflux device, and reacting for 3 hours;
(3) stopping heating, continuing stirring, and cooling the solution to room temperature to obtain the modified grinding-aid early strength agent.
In the modified grinding-aid early strength agent product obtained in the embodiment, the mass ratio of the ester compound, the polyacrylic acid, the alcohol amine monomer and the acrylic acid monomer is 63.4%, 12.5%, 16% and 8.1% respectively in the organic matter according to the determination of the liquid chromatography.
Example 3
A modified grinding-assisted early strength agent using steel slag is characterized by comprising the following raw materials in parts by weight:
55 parts of diisopropanolamine;
45 parts of acrylic acid;
110 parts of water;
the preparation method is shown as a flow chart in figure 1 and comprises the following steps:
(1) weighing the raw materials according to the proportion, and putting the raw materials into a round-bottom flask to be uniformly mixed;
(2) putting the round-bottom flask into a magnetic stirrer, wherein the rotating speed is 600r/min, the temperature is 80 ℃, adding a condensation reflux device, and reacting for 4 hours;
(3) stopping heating, continuing stirring, and cooling the solution to room temperature to obtain the modified grinding-aid early strength agent.
In the modified grinding-aid early strength agent product obtained in the embodiment, the mass ratio of the ester compound, the polyacrylic acid, the alcohol amine monomer and the acrylic acid monomer is 74.6%, 14.1%, 10.2% and 1.1%, respectively, in the organic matter as determined by liquid chromatography.
Example 4
A modified grinding-assisted early strength agent using steel slag is characterized by comprising the following raw materials in parts by weight:
55 parts of diethanol amine;
45 parts of acrylic acid;
110 parts of water;
the preparation method is shown as a flow chart in figure 1 and comprises the following steps:
(1) weighing the raw materials according to the proportion, and putting the raw materials into a round-bottom flask to be uniformly mixed;
(2) putting the round-bottom flask into a magnetic stirrer, wherein the rotating speed is 500r/min, the temperature is 70 ℃, adding a condensation reflux device, and reacting for 3 hours;
(3) stopping heating, continuing stirring, and cooling the solution to room temperature to obtain the modified grinding-aid early strength agent.
In the modified grinding-aid early strength agent product obtained in the embodiment, the mass ratio of the ester compound, the polyacrylic acid, the alcohol amine monomer and the acrylic acid monomer is 69.8%, 12.9%, 14.0% and 3.3%, respectively, in the organic matter as determined by liquid chromatography.
Example 5
A modified grinding-assisted early strength agent using steel slag is characterized by comprising the following raw materials in parts by weight:
50 parts of diisopropanolamine;
45 parts of acrylic acid;
110 parts of water;
the preparation method is shown as a flow chart in figure 1 and comprises the following steps:
(1) weighing the raw materials according to the proportion, and putting the raw materials into a round-bottom flask to be uniformly mixed;
(2) putting the round-bottom flask into a magnetic stirrer, wherein the rotating speed is 400r/min, the temperature is 70 ℃, adding a condensation reflux device, and reacting for 3 hours;
(3) stopping heating, continuing stirring, and cooling the solution to room temperature to obtain the modified grinding-aid early strength agent.
In the modified grinding-aid early strength agent product obtained in the embodiment, the mass ratio of the ester compound, the polyacrylic acid, the alcohol amine monomer and the acrylic acid monomer is 69.2%, 13.3%, 15.7% and 1.8%, respectively, in the organic matter as determined by liquid chromatography.
Effects of use
When the gelled material with the solid waste addition amount of more than 90 percent and the steel slag addition amount of more than 50 percent is ground, spraying the modified grinding-assisted early strength agent prepared in the embodiments 1-5 of the invention with the mass of 0.03 percent of the mass of the gelled material; preparing foam slurry with the average pore diameter of 1mm by using a micro-bubble generating device; mixing the powder grinding material and the foam slurry, and adding a proper amount of water reducing agent; after pouring and curing, the prepared density is 820kg/m3A light wall material. Compared with the method without adding the reagent, the using effect of the product is shown in the table 2.
TABLE 2 use effect of the lightweight wall material product of the present invention
The above description is a more detailed description of the present invention with reference to specific preferred embodiments, and it is not intended to limit the present invention to the specific embodiments described above. It will be apparent to those skilled in the art that various modifications, additions, substitutions, and the like can be made without departing from the spirit of the invention.
Claims (9)
1. A modified grinding-aid early strength agent for steel slag is characterized by comprising (a) 60% -75% of ester compounds by the total weight of the modified grinding-aid early strength agent, (b) 5% -15% of polyacrylic acid by the total weight of the modified grinding-aid early strength agent, and (c) 10% -35% of alcohol amine and acrylic acid monomers by the total weight of the modified grinding-aid early strength agent.
2. The modified grinding-aid early strength agent for steel slag according to claim 1, which is characterized in that: the ester compound is an alcohol amine and an acrylic acid esterification product.
3. The preparation method of the modified early grinding-assisting agent for steel slag as claimed in claim 1 or 2, which is characterized in that: adding water into the alcohol amine and the acrylic acid, uniformly mixing, heating while stirring, reacting for 3-4 h at the temperature of 60-80 ℃, and cooling the solution to room temperature to obtain the modified grinding-assisted early strength agent.
4. The preparation method of the modified grinding-aid early strength agent for steel slag according to claim 3, which is characterized by comprising the following steps: the alcohol amine, the acrylic acid and the water are respectively in parts by weight:
35-55 parts of alcohol amine;
40-50 parts of acrylic acid;
50-120 parts of water.
5. The preparation method of the modified grinding-aid early strength agent for steel slag according to claim 3, which is characterized by comprising the following steps: the alcohol amine is any one alcohol compound of diethanolamine, triethanolamine, dipropanol amine, tripropanol amine, diisopropanol amine, triisopropanol amine and dibutanol amine.
6. The preparation method of the modified grinding-aid early strength agent for steel slag according to claim 3, which is characterized by comprising the following steps: the mixture was stirred with a magnetic stirrer.
7. The preparation method of the modified grinding-aid early strength agent for steel slag according to claim 6, which is characterized in that: the rotating speed of stirring is 350 r/min-550 r/min.
8. The application method of the modified early grinding-assisting agent for the steel slag as claimed in claim 1 or 2 is characterized in that: the modified grinding-aid early strength agent is diluted by water and is uniformly sprayed or dripped on the surface of the raw material, and the dosage of the modified grinding-aid early strength agent is 0.01-0.07 percent of the weight of the ground cementing material.
9. The application method of the steel slag modified grinding-aid early strength agent according to claim 8, which is characterized in that: in the cementing material, the addition amount of the steel slag is more than 50 percent of the total weight of the cementing material.
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