CN110330255B - Coagulation-promoting liquid grinding aid and preparation method thereof - Google Patents
Coagulation-promoting liquid grinding aid and preparation method thereof Download PDFInfo
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- CN110330255B CN110330255B CN201910589866.3A CN201910589866A CN110330255B CN 110330255 B CN110330255 B CN 110330255B CN 201910589866 A CN201910589866 A CN 201910589866A CN 110330255 B CN110330255 B CN 110330255B
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- 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
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- 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
- C04B2103/52—Grinding aids; Additives added during grinding
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Abstract
The invention discloses a coagulation promoting type liquid grinding aid and a preparation method thereof, belonging to the technical field of cement additives. The grinding aid is prepared from the following raw materials in parts by mass: 5-15% of aluminum sulfate, 5-10% of magnesium sulfate, 40-50% of modified alcohol amine organic micromolecules, 3-10% of sodium lignosulphonate, 1.5-3% of calcium formate and the balance of deionized water. The invention uses the mixture of aluminum sulfate and magnesium sulfate as the main component of accelerating the cement hydration process; the chemical imbalance caused by the high content of aluminum ions leads to gypsum and C3A is easier to dissolve, and the generation of a large amount of early ettringite is promoted, so that the effect of quick setting is achieved; the modified alcamines organic micromolecules as grinding-aid reinforcing components have good stability, simple preparation process and mild reaction. The liquid grinding aid provided by the invention can be used for quickly coagulating cement in the early stage, simultaneously ensuring the early strength, not influencing the later strength increase and having good adaptability to cement.
Description
Technical Field
The invention belongs to the technical field of cement additives, and particularly relates to a coagulation accelerating type liquid grinding aid and a preparation method thereof.
Background
The grinding aid is an additive which is used in cement concrete, can obviously improve the grinding efficiency of a grinding machine, reduce the electric energy consumption and the steel ball loss, improve the cement yield, can effectively shorten the grinding time, improve the cement performance, save energy and reduce emission, and becomes a well-known important cement additive. The cement grinding aid can be adsorbed on high-energy active points of broken fine grains of the particles, free energy is reduced, and meanwhile the cement grinding aid permeates into fine grain gaps to provide external ions or molecules, so that the electrostatic effect of powder is reduced, coalescence is prevented, the specific surface area of cement is increased, and the content of cement particles with the particle size of 3-32 mu m is increased.
The cement grinding aid is a general term for adding chemical agents into a system in the cement clinker grinding process. The cement grinding aids are divided into powder grinding aids and liquid grinding aids. Because the required addition amount of the powder grinding aid is high, and the grinding aid mainly comprises industrial pure composite organic salt and inorganic salt, the utilization rate of the powder grinding aid is gradually reduced; the liquid grinding aid has low content of salt ions and is convenient to add, so that the liquid grinding aid is widely applied to the current cement production.
At present, triethanolamine is one of main raw materials of a grinding aid and accounts for about 70 percent of the total amount of the formula of the grinding aid, the mixing amount of the compound cement grinding aid sold in the market is large, and simultaneously, along with the price rise of chemical raw materials such as petroleum, the price of the triethanolamine is also rising, so that the product cost of the grinding aid is higher, and the popularization and the application of the cement grinding aid are severely restricted; meanwhile, the quality of the grinding aid sold in the market at present is unstable, and the mixing amount is large, so that the quality of cement fluctuates, and the performance is unstable.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a coagulation accelerating liquid grinding aid and a preparation method thereof, the grinding aid can effectively shorten the cement quick-setting time, simultaneously ensure the early strength of cement, and has good adaptability, simple and practical preparation method and energy conservation.
The technical scheme adopted by the invention is as follows:
the coagulation-promoting liquid grinding aid is prepared from the following raw materials in parts by mass: 5-15% of aluminum sulfate, 5-10% of magnesium sulfate, 40-50% of modified alcohol amine organic micromolecules, 3-10% of sodium lignosulfonate, 1.5-3% of calcium formate and the balance of deionized water;
the modified alcamines organic micromolecules are prepared by the following method: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 30-80 ℃, reacting for 1-3h under the action of a catalyst, and then adding organic acid into the obtained solution to react for 0.5-2h to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 1-3: 2-6: 0.001-0.005: 2-5.
Preferably, the polyamine is one of ethylenediamine, p-phenylenediamine, 1, 4-butanediamine, neopentyldiamine, decamethylenediamine or 2-methylpentylenediamine.
Preferably, the epoxy organic small molecule is one of ethylene oxide, propylene oxide, 1, 2-butylene oxide and 1, 2-pentylene oxide.
Preferably, the catalyst is one of ferric chloride, aluminum chloride, stannic chloride or zinc chloride.
Preferably, the organic acid is one of formic acid, acetic acid, oxalic acid, citric acid, salicylic acid or benzoic acid.
Preferably, the aluminum sulfate is industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
Preferably, the magnesium sulfate is industrial grade, and the content of magnesium oxide is more than or equal to 16.20%.
Preferably, the sodium lignosulfonate is of industrial grade, and the effective content is more than or equal to 99.00%.
Preferably, the calcium formate is in industrial grade, and the effective content is more than or equal to 98.00%.
A preparation method of a coagulation promoting type liquid grinding aid comprises the following steps:
(1) preparing the modified alcohol amine organic micromolecules: putting polyamines and epoxy organic micromolecules into a reaction container, heating to 35-80 ℃, reacting for 1-3h under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1-2h to obtain modified alcoholamines organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 1-3: 2-6: 0.001-0.005: 2-5;
(2) putting aluminum sulfate and magnesium sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 0.5-1h at 400r/min in a constant-temperature water bath at 65-85 ℃ to obtain a quick-setting mother liquor; stirring at 350r/min in a constant-temperature water bath at 60-75 ℃, adding the modified alcohol amine organic micromolecules into the quick-setting mother liquor, continuously stirring for 45min, then adding calcium formate, stirring at 65-70 ℃ for 40min under heat preservation, cooling to room temperature, adding sodium lignin sulfonate, and stirring at 300r/min for 30min to obtain the liquid grinding aid.
Has the advantages that:
(1) the liquid grinding aid has scientific formula and reasonable proportion, the aluminum sulfate and the magnesium sulfate used in the invention are mixed to be used as the main coagulation accelerating component, and the introduced magnesium ions can be preferentially combined with OH in the hydration process of cement-Formation of Mg (OH)2Becoming nucleation particles to accelerate the hydration process of cement; the chemical imbalance caused by the high content of aluminum ions leads to gypsum and C3A is easier to dissolve, and the generation of a large amount of early ettringite is promoted, so that the effect of quick setting is achieved; the calcium formate can effectively improve the coagulation accelerating and early strength performances; the modified alcamines organic micromolecules are used as grinding-aid reinforcing components, so that the cement grinding aid has good stability, the micromolecule form is easier to enter cracks of cement particles and be adsorbed on the particle surface, and the surface energy of the particles is effectively reduced, so that the hardness and the strength of the material are changed; the preparation method of the modified alcohol amine has the advantages of simple process, mild reaction and easy realization of amplification experiments.
(2) The liquid grinding aid provided by the invention is added according to the traditional use method of the grinding aid, so that the early-stage rapid coagulation of cement can be realized, the early-stage strength can be ensured, the later-stage strength increase is not influenced, and the adaptability to the cement is good.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
The coagulation-promoting liquid grinding aid is prepared from the following raw materials in parts by mass: 5% of aluminum sulfate, 5% of magnesium sulfate, 40% of modified alcohol amine organic micromolecules, 3% of sodium lignosulfonate, 1.5% of calcium formate and the balance of deionized water;
the modified alcamines organic micromolecules are prepared by the following method: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 30 ℃, reacting for 1h under the action of a catalyst, and then adding organic acid into the obtained solution to react for 0.5h to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 1: 2: 0.001: 2.
the polyamine is ethylenediamine.
The epoxy organic micromolecules are ethylene oxide.
The catalyst is ferric chloride.
The organic acid is formic acid.
The aluminum sulfate is of industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the content of magnesium oxide is more than or equal to 16.20 percent.
The sodium lignosulfonate is of industrial grade, and the effective content is more than or equal to 99.00%.
The calcium formate is in industrial grade, and the effective content is more than or equal to 98.00 percent.
A preparation method of a coagulation promoting type liquid grinding aid comprises the following steps:
(1) preparing the modified alcohol amine organic micromolecules: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 35 ℃, reacting for 1h under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1h to obtain modified alkanolamine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 1: 2: 0.001: 2;
(2) putting aluminum sulfate and magnesium sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 0.5h at 400r/min in a constant-temperature water bath at 65 ℃ to obtain a quick-setting mother solution; stirring at 350r/min in a constant-temperature water bath at 60 ℃, adding the modified alcohol amine organic micromolecules into the quick-setting mother liquor, continuously stirring for 45min, then adding calcium formate, stirring at 65 ℃ for 40min under heat preservation, cooling to room temperature, adding sodium lignosulfonate, and stirring at 300r/min for 30min to obtain the liquid grinding aid in the embodiment.
Example 2
The coagulation-promoting liquid grinding aid is prepared from the following raw materials in parts by mass: 7% of aluminum sulfate, 7% of magnesium sulfate, 42% of modified alcohol amine organic micromolecules, 5% of sodium lignosulfonate, 2% of calcium formate and the balance of deionized water;
the modified alcamines organic micromolecules are prepared by the following method: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 35 ℃, reacting for 1.5 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1 hour to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 1.5: 3: 0.0015: 3.
the polyamine is p-phenylenediamine.
The epoxy organic micromolecules are propylene oxide.
The catalyst is aluminum chloride.
The organic acid is acetic acid.
The aluminum sulfate is of industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the content of magnesium oxide is more than or equal to 16.20 percent.
The sodium lignosulfonate is of industrial grade, and the effective content is more than or equal to 99.00%.
The calcium formate is in industrial grade, and the effective content is more than or equal to 98.00 percent.
A preparation method of a coagulation promoting type liquid grinding aid comprises the following steps:
(1) preparing the modified alcohol amine organic micromolecules: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 35 ℃, reacting for 1.5 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1 hour to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 1.5: 3: 0.0015: 3.
(2) putting aluminum sulfate and magnesium sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 0.8h at 400r/min in a constant-temperature water bath at 70 ℃ to obtain a quick-setting mother solution; stirring at 350r/min in a constant-temperature water bath at 70 ℃, adding the modified alcohol amine organic micromolecules into the quick-setting mother liquor, continuously stirring for 45min, then adding calcium formate, stirring at 67 ℃ for 40min under heat preservation, cooling to room temperature, adding sodium lignosulfonate, and stirring at 300r/min for 30min to obtain the liquid grinding aid of the embodiment.
Example 3
The coagulation-promoting liquid grinding aid is prepared from the following raw materials in parts by mass: 8% of aluminum sulfate, 8% of magnesium sulfate, 43% of modified alcohol amine organic micromolecules, 6% of sodium lignosulfonate, 2% of calcium formate and the balance of deionized water;
the modified alcamines organic micromolecules are prepared by the following method: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 45 ℃, reacting for 2 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1.5 hours to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 2: 4: 0.002: 3.
the polyamine is 1, 4-butanediamine.
The epoxy organic micromolecules are 1, 2-epoxybutane.
The catalyst is tin chloride.
The organic acid is oxalic acid.
The aluminum sulfate is of industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the content of magnesium oxide is more than or equal to 16.20 percent.
The sodium lignosulfonate is of industrial grade, and the effective content is more than or equal to 99.00%.
The calcium formate is in industrial grade, and the effective content is more than or equal to 98.00 percent.
A preparation method of a coagulation promoting type liquid grinding aid comprises the following steps:
(1) preparing the modified alcohol amine organic micromolecules: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 45 ℃, reacting for 2 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1.5 hours to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 2: 4: 0.002: 3.
(2) putting aluminum sulfate and magnesium sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 0.8h at 400r/min in a constant-temperature water bath at 75 ℃ to obtain a quick-setting mother solution; stirring at 350r/min in a constant-temperature water bath at 70 ℃, adding the modified alcohol amine organic micromolecules into the quick-setting mother liquor, continuously stirring for 45min, then adding calcium formate, stirring at 68 ℃ for 40min under heat preservation, cooling to room temperature, adding sodium lignosulfonate, and stirring at 300r/min for 30min to obtain the liquid grinding aid of the embodiment.
Example 4
The coagulation-promoting liquid grinding aid is prepared from the following raw materials in parts by mass: 10% of aluminum sulfate, 8% of magnesium sulfate, 45% of modified alcohol amine organic micromolecules, 7% of sodium lignosulfonate, 2.5% of calcium formate and the balance of deionized water;
the modified alcamines organic micromolecules are prepared by the following method: putting polyamines and epoxy organic micromolecules into a reaction container, heating to 55 ℃, reacting for 2.5 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1.5 hours to obtain modified alcoholamines organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 2.5: 5: 0.003: 4.
the polyamine is neopentylene diamine.
The epoxy organic micromolecules are 1, 2-epoxy pentane.
The catalyst is zinc chloride.
The organic acid is citric acid.
The aluminum sulfate is of industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the content of magnesium oxide is more than or equal to 16.20 percent.
The sodium lignosulfonate is of industrial grade, and the effective content is more than or equal to 99.00%.
The calcium formate is in industrial grade, and the effective content is more than or equal to 98.00 percent.
A preparation method of a coagulation promoting type liquid grinding aid comprises the following steps:
(1) preparing the modified alcohol amine organic micromolecules: putting polyamines and epoxy organic micromolecules into a reaction container, heating to 55 ℃, reacting for 2.5 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1.5 hours to obtain modified alcoholamines organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 2.5: 5: 0.003: 4.
(2) putting aluminum sulfate and magnesium sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 0.8h at 400r/min in a constant-temperature water bath at 80 ℃ to obtain a quick-setting mother solution; stirring at 350r/min in a constant-temperature water bath at 70 ℃, adding the modified alcohol amine organic micromolecules into the quick-setting mother liquor, continuously stirring for 45min, then adding calcium formate, stirring at 68 ℃ for 40min under heat preservation, cooling to room temperature, adding sodium lignosulfonate, and stirring at 300r/min for 30min to obtain the liquid grinding aid of the embodiment.
Example 5
The coagulation-promoting liquid grinding aid is prepared from the following raw materials in parts by mass: 12% of aluminum sulfate, 8% of magnesium sulfate, 48% of modified alcohol amine organic micromolecules, 8% of sodium lignosulfonate, 2.5% of calcium formate and the balance of deionized water;
the modified alcamines organic micromolecules are prepared by the following method: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 70 ℃, reacting for 2 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1.5 hours to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 2: 5: 0.003: 3.
the polyamine is decamethylenediamine.
The epoxy organic micromolecules are ethylene oxide.
The catalyst is ferric chloride.
The organic acid is salicylic acid.
The aluminum sulfate is of industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the content of magnesium oxide is more than or equal to 16.20 percent.
The sodium lignosulfonate is of industrial grade, and the effective content is more than or equal to 99.00%.
The calcium formate is in industrial grade, and the effective content is more than or equal to 98.00 percent.
A preparation method of a coagulation promoting type liquid grinding aid comprises the following steps:
(1) preparing the modified alcohol amine organic micromolecules: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 70 ℃, reacting for 2 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 1.5 hours to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 2: 5: 0.003: 3.
(2) putting aluminum sulfate and magnesium sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 0.8h at 400r/min in a constant-temperature water bath at 80 ℃ to obtain a quick-setting mother solution; stirring at 350r/min in a constant-temperature water bath at 70 ℃, adding the modified alcohol amine organic micromolecules into the quick-setting mother liquor, continuously stirring for 45min, then adding calcium formate, stirring at 68 ℃ for 40min under heat preservation, cooling to room temperature, adding sodium lignosulfonate, and stirring at 300r/min for 30min to obtain the liquid grinding aid of the embodiment.
Example 6
The coagulation-promoting liquid grinding aid is prepared from the following raw materials in parts by mass: 15% of aluminum sulfate, 10% of magnesium sulfate, 50% of modified alcohol amine organic micromolecules, 10% of sodium lignosulfonate, 3% of calcium formate and the balance of deionized water;
the modified alcamines organic micromolecules are prepared by the following method: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 80 ℃, reacting for 3 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 2 hours to obtain modified alkanolamine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 3: 6: 0.005: 5.
the polyamine is 2-methyl pentanediamine.
The epoxy organic micromolecules are propylene oxide.
The catalyst is aluminum chloride.
The organic acid is benzoic acid.
The aluminum sulfate is of industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the content of magnesium oxide is more than or equal to 16.20 percent.
The sodium lignosulfonate is of industrial grade, and the effective content is more than or equal to 99.00%.
The calcium formate is in industrial grade, and the effective content is more than or equal to 98.00 percent.
A preparation method of a coagulation promoting type liquid grinding aid comprises the following steps:
(1) preparing the modified alcohol amine organic micromolecules: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 80 ℃, reacting for 3 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 2 hours to obtain modified alkanolamine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 3: 6: 0.005: 5;
(2) putting aluminum sulfate and magnesium sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 1h at 400r/min in a constant-temperature water bath at 85 ℃ to obtain a quick-setting mother liquor; stirring at 350r/min in a constant-temperature water bath at 75 ℃, adding the modified alcohol amine organic micromolecules into the quick-setting mother liquor, continuously stirring for 45min, then adding calcium formate, stirring at 70 ℃ for 40min under heat preservation, cooling to room temperature, adding sodium lignosulfonate, and stirring at 300r/min for 30min to obtain the liquid grinding aid in the embodiment.
Comparative example 1
The coagulation-promoting liquid grinding aid is prepared from the following raw materials in parts by mass: 15% of aluminum sulfate, 50% of modified alcohol amine organic micromolecules, 10% of sodium lignosulfonate, 3% of calcium formate and the balance of deionized water;
the modified alcamines organic micromolecules are prepared by the following method: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 80 ℃, reacting for 3 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 2 hours to obtain modified alkanolamine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 3: 6: 0.005: 5.
the polyamine is 2-methyl pentanediamine.
The epoxy organic micromolecules are propylene oxide.
The catalyst is aluminum chloride.
The organic acid is benzoic acid.
The aluminum sulfate is of industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the content of magnesium oxide is more than or equal to 16.20 percent.
The sodium lignosulfonate is of industrial grade, and the effective content is more than or equal to 99.00%.
The calcium formate is in industrial grade, and the effective content is more than or equal to 98.00 percent.
A preparation method of a coagulation promoting type liquid grinding aid comprises the following steps:
(1) preparing the modified alcohol amine organic micromolecules: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 80 ℃, reacting for 3 hours under the action of a catalyst, and then adding organic acid into the obtained solution to react for 2 hours to obtain modified alkanolamine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 3: 6: 0.005: 5;
(2) putting aluminum sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 1h at 400r/min in a constant-temperature water bath at 85 ℃ to obtain a quick-setting mother liquor; and stirring at 350r/min in a constant-temperature water bath at 75 ℃, adding the modified alcohol amine organic micromolecules into the quick-setting mother liquor, continuously stirring for 45min, then adding calcium formate, stirring at 70 ℃ for 40min under heat preservation, cooling to room temperature, adding sodium lignosulfonate, and stirring for 30min at 300r/min to obtain the liquid grinding aid of the comparative example. The formula of the raw materials and the preparation method of the grinding aid of the comparative example are the same as those of example 6 except that magnesium sulfate is not added.
Comparative example 2
The formula and preparation method of the raw materials of the grinding aid of the comparative example are the same as those of example 6 except that aluminum sulfate is not added.
Comparative example 3
The coagulation-promoting liquid grinding aid is prepared from the following raw materials in parts by mass: 15% of aluminum sulfate, 10% of magnesium sulfate, 10% of sodium lignosulfonate, 3% of calcium formate and the balance of deionized water;
the polyamine is 2-methyl pentanediamine.
The epoxy organic micromolecules are propylene oxide.
The catalyst is aluminum chloride.
The organic acid is benzoic acid.
The aluminum sulfate is of industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
The magnesium sulfate is of industrial grade, and the content of magnesium oxide is more than or equal to 16.20 percent.
The sodium lignosulfonate is of industrial grade, and the effective content is more than or equal to 99.00%.
The calcium formate is in industrial grade, and the effective content is more than or equal to 98.00 percent.
A preparation method of a coagulation promoting type liquid grinding aid comprises the following steps:
(1) putting aluminum sulfate and magnesium sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 1h at 400r/min in a constant-temperature water bath at 85 ℃ to obtain a quick-setting mother liquor; stirring at 350r/min for 45min under the constant-temperature water bath of 75 ℃, then adding calcium formate, stirring at 70 ℃ for 40min under the condition of heat preservation, cooling to room temperature, adding sodium lignosulfonate, and stirring at 300r/min for 30min to obtain the liquid grinding aid of the comparative example.
The formula and the preparation method of the raw materials of the grinding aid are the same as those of the grinding aid in example 6 except that the grinding aid does not contain the modified alcohol amine organic micromolecules.
Performance testing
The cement grinding aid obtained by the invention is tested in a standard test small mill with 5kg phi 500 multiplied by 500mm, and the concrete process is as follows:
the test is carried out according to the following material ratio: 80 parts by mass of clinker, 5 parts by mass of dihydrate gypsum, 11 parts by mass of fly ash and 4 parts by mass of limestone, mixing the materials, adding the coagulation promoting liquid grinding aid obtained by the invention with the mass fraction of 0.5% of the mixture into the obtained mixture, and mixing and grinding for 26min to obtain the cement.
Carrying out cement mortar strength detection according to GB/T17671-1999 method for testing cement mortar strength (ISO method); measuring the specific surface area of the cement according to GB/T8074 method for measuring specific surface area of cement (Brinell method); and detecting the standard consistency and the setting time of the cement according to GB/T1346 detection method for water consumption, setting time and stability of the standard consistency of the cement.
The liquid grinding aids of accelerating coagulation type obtained in examples 1-6 and comparative examples 1-3 were subjected to small grinding test, and a blank example was set, i.e., no grinding aid was added. And a commercial grinding aid test set was set up, i.e., using a commercial conventional grinding aid. The test results are shown in Table 1.
TABLE 1 Small grind test data for accelerating liquid grinding aid
As can be seen from the data in Table 1, the prepared coagulation promoting liquid grinding aids of examples 1 to 6 have good coagulation promoting effect, greatly shorten the coagulation time of cement, have obvious grinding aiding effect and increase about 10 points on average; and the compressive strength of 1d is higher, the 4-5MPa can be improved, the strength increase rate of 28d is obviously improved, and the grinding aid has an enhancement effect on cement in the later period and achieves the expected effect.
Through comparison of the performance tests of the test examples with those of comparative examples 1 to 3, it can be seen that the setting time of the comparative examples is shortened with the loss of the main quick-setting component and the grinding aid enhancing component, but the change amplitude is obviously smaller, the 3d strength is not as high as that of the examples, and the 28d strength is lost. Tests show that each main component of the product can play an individual role, the effect of the product is obvious for the examples, and the product can play the best role by the coordinated and superimposed effect generated by the main components and the examples.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Claims (6)
1. The coagulation-accelerating liquid grinding aid is characterized by being prepared from the following raw materials in parts by mass: 5-15% of aluminum sulfate, 5-10% of magnesium sulfate, 40-50% of modified alcohol amine organic micromolecules, 3-10% of sodium lignosulfonate, 1.5-3% of calcium formate and the balance of deionized water;
the modified alcamines organic micromolecules are prepared by the following method: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 30-80 ℃, reacting for 1-3h under the action of a catalyst, and then adding organic acid into the obtained solution to react for 0.5-2h to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 1-3: 2-6: 0.001-0.005: 2-5;
the polyamine is one of ethylenediamine, p-phenylenediamine, 1, 4-butanediamine, neopentylene diamine, decamethylene diamine or 2-methyl pentamethylene diamine;
the epoxy organic micromolecules are one of ethylene oxide, propylene oxide, 1, 2-butylene oxide and 1, 2-epoxypentane;
the catalyst is one of ferric chloride, aluminum chloride, stannic chloride or zinc chloride;
the organic acid is one of formic acid, acetic acid, oxalic acid, citric acid, salicylic acid or benzoic acid.
2. The accelerating liquid grinding aid of claim 1, wherein the aluminum sulfate is industrial grade, and the mass fraction of the aluminum oxide is more than or equal to 16.00%.
3. The accelerating-coagulation liquid grinding aid of claim 1, wherein the magnesium sulfate is industrial grade, and the content of magnesium oxide is more than or equal to 16.20%.
4. The accelerating liquid grinding aid of claim 1, wherein the sodium lignosulfonate is of industrial grade and has an active ingredient content of more than or equal to 99.00%.
5. The coagulation promoting liquid grinding aid of claim 1, wherein the calcium formate is industrial grade, and the content of active ingredients is more than or equal to 98.00%.
6. A method for preparing the accelerating liquid grinding aid of any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) preparing the modified alcohol amine organic micromolecules: placing polyamines and epoxy organic micromolecules into a reaction container, heating to 30-80 ℃, reacting for 1-3h under the action of a catalyst, and then adding organic acid into the obtained solution to react for 0.5-2h to obtain modified alcohol amine organic micromolecules; the molar ratio of the polyamine, the epoxy organic micromolecule, the catalyst and the organic acid is as follows: 1-3: 2-6: 0.001-0.005: 2-5;
(2) putting aluminum sulfate and magnesium sulfate into a three-neck flask according to the proportion, adding deionized water, and stirring for 0.5-1h at 400r/min in a constant-temperature water bath at 65-85 ℃ to obtain a quick-setting mother liquor; stirring at 350r/min in a constant-temperature water bath at 60-75 ℃, adding the modified alcohol amine organic micromolecules into the quick-setting mother liquor, continuously stirring for 45min, then adding calcium formate, stirring at 65-70 ℃ for 40min under heat preservation, cooling to room temperature, adding sodium lignin sulfonate, and stirring at 300r/min for 30min to obtain the liquid grinding aid.
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| CN111410452B (en) * | 2020-03-19 | 2022-02-08 | 云南森博混凝土外加剂有限公司 | Polyaluminium sulfate series accelerator and sprayed concrete containing same |
| CN111470796B (en) * | 2020-03-31 | 2022-03-15 | 辽宁天宝华瑞建材有限公司 | Cement grinding aid |
| CN112851177B (en) * | 2021-03-27 | 2022-04-26 | 唐山冀东水泥外加剂有限责任公司 | Cement grinding aid and cement using same |
| CN115403283B (en) * | 2022-10-08 | 2023-08-22 | 和县新城商品混凝土有限责任公司 | High early strength cement and processing method thereof |
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