Liquid grinding aid for superfine slag powder and preparation method of liquid grinding aid

Abstract

The invention discloses a liquid grinding aid for superfine slag powder, and further discloses a preparation method of the liquid grinding aid for the superfine slag powder. The liquid grinding aid is prepared from the following raw materials: 50 to 70 percent of industrial waste liquid, 2 to 10 percent of organosiloxane, 2 to 10 percent of polyhydric alcohol, 2 to 10 percent of alcohol amine substances and 10 to 30 percent of auxiliaries. Wherein the industrial waste liquid contains at least one of a carboxyl group, a hydroxyl group, an ester group and an epoxy group. According to the prepared liquid grinding aid, the industrial waste liquid is used as a main raw material, the specific surface area of the superfine slag powder in the slag grinding process is increased through the action of various groups, the activity of the superfine slag powder is improved, and the dispersity and fluidity of the slag are also improved.

Description

Technical Field

[0001] The invention relates to the field of slag micropowder grinding aids, and in particular to a liquid grinding aid for slag micropowder and a preparation method thereof. Background Art

[0002] Slag is a byproduct of high-temperature iron smelting with CaO, SiO2 and Al2O3 as the main components. It has become the preferred cement admixture for producing high-quality cement and improving the service life of concrete because it can promote the secondary hydration reaction of cement and serve as the microcrystalline nucleus of the cement hydration system. However, the components and proportions of slag and cement clinker are different, resulting in inconsistent hardness of slag and cement clinker. Therefore, when slag is ground together with cement clinker, under the same grinding conditions, the particle fineness of slag cannot reach the fineness of its optimal potential activity release. Therefore, slag needs to be ground separately.

[0003] However, due to the vitreous structure of slag, grinding aids need to be added during the slag grinding process to maintain the dispersion of slag powder during the grinding process and improve the grinding efficiency of slag powder. At present, the commonly used slag grinding aids are mainly obtained by simple compounding of water reducers, polyols, alcohol amines and other substances, but these raw materials are mostly industrial raw materials. With the implementation of economic and environmental protection requirements and energy conservation and emission reduction requirements, finding an environmentally friendly, relatively low-cost, and good grinding aid grinding aid has great practical significance for the cement and concrete industry. Summary of the invention

[0004] In order to solve the above technical problems, the first aspect of the present invention proposes a liquid grinding aid for slag micropowder, the raw materials of which include industrial waste liquid, organosiloxane, polyol, alcohol amine substance and additives.

[0005] Preferably, the industrial waste liquid contains at least one of a carboxyl group, a hydroxyl group, an ester group, an amino group, a sulfonic acid group, and an epoxy group.

[0006] Preferably, the industrial waste liquid contains at least one of a carboxyl group, a hydroxyl group, an ester group, and an epoxy group.

[0007] Preferably, the organosiloxane is polydimethylsiloxane.

[0008] Preferably, the polyol includes at least one of ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and glycerol.

[0009] Preferably, the alcoholamine substance includes at least one of monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, and diethanolmonoisopropanolamine.

[0010] Preferably, the auxiliary agent includes at least one of carbonate, phosphate, silicate, sulfate and wood calcium.

[0011] Preferably, the auxiliary agent includes at least one of carbonate, phosphate and sulfate.

[0012] The second aspect of the present invention provides a method for preparing a liquid grinding aid for slag micropowder, the steps are as follows:

[0013] (1) Put industrial waste liquid into a container, heat it, add alcohol amines, stir evenly, and react;

[0014] (2) Add polyol, organosiloxane and auxiliary agent, stir and react, and obtain the liquid grinding aid.

[0015] Preferably, the heating temperature in step (1) is 40-60°C.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1. The liquid grinding aid for slag micropowder prepared by the present invention uses industrial waste liquid as the main raw material for preparation, fully utilizes waste liquid resources, is economical and environmentally friendly, and reduces production costs. At the same time, the grinding aid prepared by the present invention is a liquid grinding aid, which contacts the slag more fully during use, thereby improving the grinding efficiency.

[0018] 2. The liquid grinding aid for slag powder prepared by the present invention improves the grinding efficiency of slag during grinding by using waste liquid in combination with other raw materials in the grinding aid. Furthermore, the reaction between the active groups in the waste liquid and the active groups in other raw materials can break down the original glass grid structure in the slag, and prevent the groups on the cross section after the breakage from reaggregating, thereby improving the activity of the slag powder.

[0019] 3. The liquid grinding aid for slag micropowder prepared by the present invention has a simple preparation method and can be well used in a vertical mill to enhance the grinding effect. DETAILED DESCRIPTION

[0020] In order to solve the above technical problems, the first aspect of the present invention proposes a liquid grinding aid for slag micropowder, the raw materials of which include industrial waste liquid, organosiloxane, polyol, alcohol amine substance and additives.

[0021] Preferably, the raw materials of the grinding aid include, by mass percentage, 50-70% industrial waste liquid, 2-10% organic siloxane, 2-10% polyol, 2-10% alcohol amine substance, and 10-30% auxiliary agent.

[0022] Preferably, the industrial waste liquid contains at least one of a carboxyl group, a hydroxyl group, an ester group, an amino group, a sulfonic acid group, and an epoxy group.

[0023] Preferably, the industrial waste liquid contains at least one of a carboxyl group, a hydroxyl group, an ester group, and an epoxy group.

[0024] Preferably, the industrial waste liquid is industrial waste liquid containing propylene glycol.

[0025] In the present application, the source of the industrial waste liquid containing propylene glycol is not limited, and can be selected from pharmaceutical waste liquid, coal-to-ethylene glycol waste liquid, textile waste liquid, crude glycerol fermentation waste liquid, etc.

[0026] Preferably, the industrial waste liquid containing propylene glycol is crude glycerol fermentation waste liquid.

[0027] Preferably, the crude glycerol fermentation waste liquid contains propylene glycol, dipropylene glycol, tripropylene glycol and propylene oxide.

[0028] Preferably, the content of propylene oxide in the crude glycerol fermentation waste liquid is 2-5wt%.

[0029] Preferably, the organosiloxane is polydimethylsiloxane.

[0030] Preferably, the viscosity of the polydimethylsiloxane is 5000-20000 cst at 25°C.

[0031] Preferably, the polyol includes at least one of ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and glycerol.

[0032] Preferably, the polyol is at least one of dipropylene glycol, tripropylene glycol and glycerol.

[0033] Preferably, the polyol is glycerol.

[0034] Preferably, the alcoholamine substance includes at least one of monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, and diethanolmonoisopropanolamine.

[0035] Preferably, the alcoholamine substances include diethanolamine and triethanolamine.

[0036] Preferably, the mass ratio of diethanolamine to triethanolamine is (2.5-4):1.

[0037] Preferably, the mass ratio of diethanolamine to triethanolamine is (3-3.5):1.

[0038] Preferably, the auxiliary agent includes at least one of carbonate, phosphate, silicate, sulfate and wood calcium.

[0039] Preferably, the auxiliary agent includes at least one of carbonate, phosphate and sulfate.

[0040] Preferably, the carbonate includes at least one of sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate and sodium bicarbonate.

[0041] Preferably, the phosphate includes at least one of sodium phosphate, potassium phosphate, calcium phosphate, sodium polyphosphate, and sodium metaphosphate.

[0042] Preferably, the sulfate includes at least one of sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate and barium sulfate.

[0043] Preferably, the auxiliary agent includes sodium carbonate and sodium metaphosphate.

[0044] Preferably, the mass ratio of the sodium carbonate to sodium metaphosphate is (1.2-1.8):1.

[0045] Preferably, the raw materials of the grinding aid include, by mass percentage, a mixture of 50-70% crude glycerol fermentation waste liquid, 2-10% polydimethylsiloxane, 2-10% glycerol, 2.5-7% diethanolamine, 1-3% triethanolamine, and 10-30% sodium carbonate and sodium metaphosphate.

[0046] Preferably, the raw materials of the grinding aid include, by mass percentage, a mixture of 70% crude glycerol fermentation waste liquid, 7% polydimethylsiloxane, 2-10% glycerol, 2.5-7% diethanolamine, 1-3% triethanolamine, and 12% sodium carbonate and sodium metaphosphate.

[0047] Preferably, the mass ratio of propylene oxide to diethanolamine in the crude glycerol fermentation waste liquid is (1-6):1.

[0048] Preferably, the mass ratio of propylene oxide to diethanolamine in the crude glycerol fermentation waste liquid is (1-3):1.

[0049] The second aspect of the present invention provides a method for preparing a liquid grinding aid for slag micropowder, the steps are as follows:

[0050] (1) placing crude glycerol fermentation waste liquid into a container, heating it, adding an alcohol amine substance, stirring it evenly, and reacting it; (2) then adding a polyol, an organosiloxane, and an auxiliary agent, stirring it, and reacting it, thereby obtaining the liquid grinding aid.

[0051] Preferably, the heating temperature in step (1) is 40-60°C.

[0052] Preferably, the reaction time in step (1) is 100-120 min.

[0053] Preferably, the stirring temperature in step (2) is 50-60°C.

[0054] Preferably, the stirring time in step (2) is 60-100 min.

[0055] The applicant has found through experiments that using crude glycerol fermentation waste liquid as the main raw material and adding raw materials such as alcohol amines, organosiloxanes, and polyols can improve the grinding efficiency of slag during grinding and can also improve the activity of slag. The applicant speculates that the possible reason is that the active groups such as epoxy groups contained in the crude glycerol fermentation waste liquid react with the alcohol amines added in this application at 40-50°C to generate products that have the effect of promoting the grinding efficiency of slag, and the unreacted epoxy groups in the crude glycerol fermentation waste liquid may also react with the organosiloxane added in this application to change the type of active groups on the organosiloxane, so that during the grinding process of slag, the chemical bonds on the surface of the slag micro-powder particles are broken, and the groups on the cross-section of the slag micro-powder particles are reduced through intermolecular forces. Attract each other, resulting in powder agglomeration. In addition, the applicant found during the experiment that when the mass ratio of propylene oxide to diethanolamine in the crude glycerol fermentation waste liquid is (1-3):1, the activity of the obtained slag powder is improved, further improving the performance of the cement using the slag powder; when the mass ratio of sodium carbonate and sodium metaphosphate added is (1.2-1.8):1, the dispersibility and fluidity of the slag can be effectively improved, and the grinding efficiency of the slag and the powder selection efficiency of the powder classifier can be improved.

[0056] The present invention is described in detail below by way of examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by professionals and technicians in this field based on the content of the present invention above still belong to the scope of protection of the present invention.

[0057] Example 1

[0058] Provided is a liquid grinding aid for slag micropowder, wherein the raw materials include, by mass percentage, 70% crude glycerol fermentation waste liquid, 7% polydimethylsiloxane, 2% glycerol, 7% diethanolamine, 2% triethanolamine, 7% sodium carbonate, and 5% sodium metaphosphate, wherein the content of propylene oxide in the crude glycerol fermentation waste liquid is 5wt%.

[0059] A method for preparing a liquid grinding aid for slag micropowder is also provided, the steps being as follows:

[0060] (1) Put the crude glycerol fermentation waste liquid into a container, heat it to 40°C, add diethanolamine and triethanolamine, and stir to react for 120 minutes;

[0061] (2) Add propylene glycol and polydimethylsiloxane into the container, heat to 55°C, and stir for 40 minutes;

[0062] (3) Finally, sodium carbonate and sodium metaphosphate were added, the temperature was cooled to room temperature, and stirred for 30 minutes to obtain the liquid grinding aid.

[0063] The polydimethylsiloxane was purchased from Shanghai Kain Chemical Co., Ltd. and had a viscosity of 10,000 cst at 25°C.

[0064] Example 2

[0065] Provided is a liquid grinding aid for slag micropowder, wherein the raw materials include, by mass percentage, 70% crude glycerol fermentation waste liquid, 7% polydimethylsiloxane, 2% glycerol, 6.75% diethanolamine, 2.25% triethanolamine, 7.5% sodium carbonate, and 4.5% sodium metaphosphate, wherein the content of propylene oxide in the crude glycerol fermentation waste liquid is 3wt%.

[0066] A method for preparing a liquid grinding aid for slag micropowder is also provided, the steps being as follows:

[0067] (1) Put the crude glycerol fermentation waste liquid into a container, heat it to 40°C, add diethanolamine and triethanolamine, and stir to react for 120 minutes;

[0068] (2) Add propylene glycol and polydimethylsiloxane into the container, heat to 55°C, and stir for 40 minutes;

[0069] (3) Finally, sodium carbonate and sodium metaphosphate were added, the temperature was cooled to room temperature, and stirred for 30 minutes to obtain the liquid grinding aid.

[0070] The polydimethylsiloxane was purchased from Shanghai Kain Chemical Co., Ltd. and had a viscosity of 10,000 cst at 25°C.

[0071] Comparative Example 1

[0072] Provided are a liquid grinding aid for slag micropowder and a preparation method of the liquid grinding aid for slag micropowder. The specific implementation method is the same as that of Example 1, except that 8.4% of diethanolamine and 0.6% of triethanolamine are used.

[0073] Comparative Example 2

[0074] Provided are a liquid grinding aid for slag micropowder and a preparation method of the liquid grinding aid for slag micropowder. The specific implementation method is the same as that of Example 1, except that 1.5% of diethanolamine and 7.5% of triethanolamine are used.

[0075] Comparative Example 3

[0076] Provided are a liquid grinding aid for slag micropowder and a preparation method of the liquid grinding aid for slag micropowder. The specific implementation method is the same as that of Example 1, except that 9% diethanolamine is used and no triethanolamine is added.

[0077] Comparative Example 4

[0078] Provided are a liquid grinding aid for slag micropowder and a preparation method of the liquid grinding aid for slag micropowder. The specific implementation method is the same as that of Example 1, except that no diethanolamine is added and 9% triethanolamine is added.

[0079] Comparative Example 5

[0080] Provided are a liquid grinding aid for slag micropowder and a preparation method of the liquid grinding aid for slag micropowder. The specific implementation method is the same as that of Example 1, except that 9% sodium carbonate and 3% sodium metaphosphate are used.

[0081] Comparative Example 6

[0082] Provided are a liquid grinding aid for slag micropowder and a preparation method of the liquid grinding aid for slag micropowder. The specific implementation method is the same as that of Example 1, except that 4% sodium carbonate and 8% sodium metaphosphate are used.

[0083] Performance Testing

[0084] The grinding aids prepared in the examples and comparative examples were added to slag of the same source and weight, and the amount of addition was 0.3% of the mass of the slag. After grinding under the same conditions, the specific surface area of ​​the slag powder was measured. The test cement obtained by mixing the slag powder mixed with the grinding aid and the reference cement in a mass ratio of 1:1 was compared with the reference cement, and the activity index and fluidity ratio of the slag powder mixed with the grinding aid were measured.

[0085] Activity index = (test cement strength / benchmark cement strength)*100%.

[0086] Fluidity ratio = (test cement fluidity / reference cement fluidity) * 100%.

[0087] The reference cement was purchased from Huachong Testing Instrument Sales and Service Department, Xinhua Street, Zhangdian.

[0088] The test data are recorded in Table 1.

[0089] Table 1

[0090]

[0091] The above is only a preferred embodiment of the present invention and is not intended to limit the invention in other forms. Any technician familiar with the profession may use the technical content disclosed above to change or modify it into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiment based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A liquid grinding aid for slag micropowder, characterized in that: The raw materials of the grinding aid include industrial waste liquid, organic siloxane, polyol, alcohol amine substances and auxiliary agents.

2. The grinding aid according to claim 1, characterized in that The industrial waste liquid contains at least one of a carboxyl group, a hydroxyl group, an ester group, an amino group, a sulfonic acid group, and an epoxy group.

3. The grinding aid according to claim 2, characterized in that The industrial waste liquid contains at least one of a carboxyl group, a hydroxyl group, an ester group and an epoxy group.

4. The grinding aid according to claim 1, characterized in that The organosiloxane is polydimethylsiloxane.

5. The grinding aid according to claim 1, characterized in that The polyol includes at least one of ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and glycerol.

6. The grinding aid according to claim 1, characterized in that The alcoholamine substance includes at least one of monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, and diethanolmonoisopropanolamine.

7. The grinding aid according to claim 1, characterized in that The auxiliary agent includes at least one of carbonate, phosphate, silicate, sulfate and wood calcium.

8. The grinding aid according to claim 7, characterized in that The auxiliary agent includes at least one of carbonate, phosphate and sulfate.

9. A method for preparing a liquid grinding aid for slag micropowder according to any one of claims 1 to 8, characterized in that: The steps are as follows: (1) Put industrial waste liquid into a container, heat it, add alcohol amines, stir evenly, and react; (2) Add polyol, organosiloxane and auxiliary agent, stir and react, and obtain the liquid grinding aid.

10. The preparation method according to claim 9, characterized in that: The heating temperature in step (1) is 40-60°C.

Images