Ultrafine slag powder grinding aid and preparation method thereof

Abstract

The present invention discloses a kind of ultrafine slag powder grinding aid and preparation method thereof, belong to the technical field of grinding admixture. The grinding aid of the present invention is prepared by including the following raw materials in parts by weight: 20-40 parts of small molecule polyether polyols, 10-20 parts of ethylene glycol and diethylene glycol mixed solution, 5-10 parts of water glass, 0.1-0.5 parts of sodium hexadecylsulfonate, 0.1-0.5 parts of defoamer and 20-40 parts of water. The present invention adopts ethylene oxide and glycolic acid to synthesize small molecule polyether polyol oligomers, which can adapt to slag of different particle sizes, achieve good adsorption and dispersion, effectively solve the agglomeration problem of slag differential during ultrafine grinding, and have a good grinding aid effect on slag. The obtained grinding aid can effectively improve the efficiency of ultrafine grinding of slag powder, shorten the time of ultrafine grinding, and increase the output by 20% per hour.

Description

Technical Field

[0001] The invention belongs to the technical field of grinding admixtures, and particularly relates to an ultrafine slag powder grinding aid and a preparation method thereof. Background Art

[0002] Slag powder is a high-quality raw material for cement. It can replace part of the clinker content in cement in equal amounts, significantly reducing production costs, reducing free calcium, and improving the qualified rate of cement stability performance. It can also be added to cement to improve the overall performance of cement. Slag powder of conventional fineness is prone to problems of low early strength and high later strength during use, and its incorporation ratio in cement production is limited. As the issue of cement carbon emissions has attracted people's attention, mineral powders of lower fineness have gradually been included in the research scope of low-carbon cement research. By reducing the fineness of slag powder, the 3D activity of mineral powder can be stimulated. Therefore, the grinding technology of ultrafine mineral powder has become a hot topic of current research. The specific surface area of ​​conventional slag powder is 400-500m 2 / kg, its hydration activity can generally be manifested after 7 days, and the slag surface area is ground to 700-1000m 2 / kg, its hydration activity can be advanced to 3 days, which can effectively increase the mixing ratio, reduce the proportion of clinker used in cement, and reduce cement production costs. Conventional cement or mineral powder grinding aids are mainly used for cement with a specific surface area of ​​less than 400-500m 2 / kg application scenario, as the specific surface area of ​​the powder increases, the surface energy of the particles is higher, and traditional grinding aids are not applicable. Special grinding aids specifically for ultrafine mineral powder grinding are needed.

[0003] In the prior art, the slag grinding aid mother liquor prepared by Chinese patent CN105154007B can significantly improve the grinding efficiency of slag and optimize the particle size distribution of ore powder without destroying the hydroxyl group with efficient grinding aid effect, but its preparation method is complicated, the raw material cost is high and complicated, and the comprehensive performance effect is not obvious. The slag grinding aid prepared by Chinese patent CN102618011B has a simple preparation method and easy-to-obtain raw materials, but when added to slag, its grinding effect is not ideal and can not fully stimulate the activity of slag micropowder. The shortcomings of the prior art are mainly the problems of insufficient grinding aid and dispersibility. Therefore, how to solve the problems in these two aspects is a technical problem that needs to be solved urgently. Summary of the Invention

[0004] The technical problem to be solved by the present invention is mainly the problem that conventional cement grinding aids have insufficient grinding and dispersing capabilities in the production of ultrafine mineral powder. The present inventors consider solving this problem by preparing small molecule polyether polyols.

[0005] In order to achieve the above technical objectives, the technical solution adopted by the present invention is:

[0006] An ultrafine slag powder grinding aid is prepared from the following raw materials in parts by weight: 20-40 parts of small molecule polyether polyol, 10-20 parts of a mixture of ethylene glycol and diethylene glycol, 5-10 parts of water glass, 0.1-0.5 parts of sodium hexadecyl sulfonate, 0.1-0.5 parts of a defoaming agent, and 20-40 parts of water.

[0007] Furthermore, the ethylene glycol and diethylene glycol mixture is a by-product of producing ethylene glycol by ethylene oxide hydration.

[0008] Furthermore, the modulus of the water glass is 3.2.

[0009] Furthermore, the defoaming agent is an organosilicon defoaming agent, model THIX-278, purchased from Yantai Hengxin Chemical Technology Co., Ltd.

[0010] Furthermore, the preparation method of the small molecule polyether polyol is:

[0011] (1) Weigh 4-6 parts of ethylene oxide and place them in a sealed jar for later use;

[0012] (2) Add 2 parts of glycolic acid to the autoclave, adjust the pH to 12 using saturated potassium hydroxide solution, and tighten the autoclave to maintain a sealed state.

[0013] (3) Using nitrogen to replace the atmosphere inside the autoclave, and then using nitrogen to press half of the ethylene oxide in the sealed tank into the autoclave. After the addition is completed, stirring for 20 minutes;

[0014] (4) Raise the temperature of the autoclave to 100-120°C, stir at 300 rpm, maintain the autoclave pressure at 2 MPa, and begin to uniformly pressurize the remaining ethylene oxide into the autoclave using nitrogen pressure for 1 hour;

[0015] (5) After the reaction is completed, the reactor is cooled to 30°C using circulating cold water and the vacuum degree is -0.02 MPa, and the unreacted ethylene oxide in the reaction system is distilled out and recycled;

[0016] (6) The materials inside the reactor are transferred out to obtain small molecule polyether polyols.

[0017] Furthermore, the grinding aid of the present invention is used in an amount of 0.05-0.15% of the mass of the slag.

[0018] A method for preparing a fine slag powder grinding aid comprises the following steps:

[0019] (1) Preparation of small molecule polyether polyols;

[0020] (2) adding small molecule polyether polyol and water into a stirring kettle and stirring evenly;

[0021] (3) Add the mixture of ethylene glycol and diethylene glycol, sodium cetyl sulfate and water glass to the stirred tank, stir quickly until uniform, then add the defoamer and continue stirring for 30 minutes;

[0022] (4) The material obtained in step (3) is filtered through a 100-mesh cloth to obtain an ultrafine slag powder grinding aid.

[0023] Beneficial effects of the present invention:

[0024] (1) The present invention uses ethylene oxide and glycolic acid to synthesize small molecule polyether polyol oligomers, and uses potassium hydroxide to catalyze the polymerization process to obtain oligomers of different molecular weights. The oligomers can adapt to slag of different particle sizes, achieve good adsorption and dispersion effects, effectively solve the problem of slag differential agglomeration during ultrafine grinding, and have a good grinding aid effect on slag;

[0025] (2) The sodium dodecyl sulfonate used in the present invention can be effectively adsorbed on the surface of the slag powder, and the hydrophobic alkyl group can play a certain lubricating role, thereby improving the sphericity of the slag powder during the ultrafine grinding process and improving the early activation effect of the slag powder;

[0026] (3) The ultrafine slag powder grinding aid of the present invention can effectively improve the efficiency of ultrafine grinding of slag powder, shorten the ultrafine grinding time, and increase the hourly output by 20%. DETAILED DESCRIPTION

[0027] The technical solution of the present invention will be further described below with reference to specific embodiments, but is not limited thereto. Example 1

[0028] An ultrafine slag powder grinding aid is prepared from the following raw materials in parts by weight: 40 parts of small molecule polyether polyol, 15 parts of a mixture of ethylene glycol and diethylene glycol, 5 parts of water glass, 0.1 part of sodium hexadecyl sulfonate, 0.1 part of a defoaming agent, and 39.8 parts of water.

[0029] The ethylene glycol and diethylene glycol mixed liquid is a by-product of producing ethylene glycol by ethylene oxide hydration.

[0030] The modulus of the water glass is 3.2.

[0031] The defoaming agent is an organosilicon defoaming agent, model THIX-278, purchased from Yantai Hengxin Chemical Technology Co., Ltd.

[0032] The preparation method of the small molecule polyether polyol is:

[0033] (1) Weigh 4 parts of ethylene oxide and place them in a sealed jar for later use;

[0034] (2) Add 2 parts of glycolic acid to the autoclave, adjust the pH to 12 using saturated potassium hydroxide solution, and tighten the autoclave to maintain a sealed state.

[0035] (3) Using nitrogen to replace the atmosphere inside the autoclave, and then using nitrogen to press half of the ethylene oxide in the sealed tank into the autoclave. After the addition is completed, stirring for 20 minutes;

[0036] (4) The temperature of the autoclave was raised to 100°C, the stirring speed was set at 300 rpm, the pressure of the autoclave was maintained at 2 MPa, and the remaining ethylene oxide was uniformly pressed into the autoclave using nitrogen pressure. The reaction time was 1 hour.

[0037] (5) After the reaction is completed, the reactor is cooled to 30°C using circulating cold water and the vacuum degree is -0.02 MPa, and the unreacted ethylene oxide in the reaction system is distilled out and recycled;

[0038] (6) The materials inside the reactor are transferred out to obtain small molecule polyether polyols.

[0039] The grinding aid in this embodiment is used in an amount of 0.05-0.15% of the mass of the slag.

[0040] A method for preparing a fine slag powder grinding aid comprises the following steps:

[0041] (1) Preparation of small molecule polyether polyols;

[0042] (2) adding small molecule polyether polyol and water into a stirring kettle and stirring evenly;

[0043] (3) Add the mixture of ethylene glycol and diethylene glycol, sodium cetyl sulfate and water glass to the stirred tank, stir quickly until uniform, then add the defoamer and continue stirring for 30 minutes;

[0044] (4) The material obtained in step (3) is filtered through a 100-mesh cloth to obtain an ultrafine slag powder grinding aid. Example 2

[0045] An ultrafine slag powder grinding aid is prepared from the following raw materials in parts by weight: 35 parts of small molecule polyether polyol, 15 parts of a mixture of ethylene glycol and diethylene glycol, 10 parts of water glass, 0.1 part of sodium hexadecyl sulfonate, 0.1 part of a defoaming agent, and 39.8 parts of water.

[0046] The ethylene glycol and diethylene glycol mixed liquid is a by-product of producing ethylene glycol by ethylene oxide hydration.

[0047] The modulus of the water glass is 3.2.

[0048] The defoaming agent is an organosilicon defoaming agent, model THIX-278, purchased from Yantai Hengxin Chemical Technology Co., Ltd.

[0049] The preparation method of the small molecule polyether polyol is:

[0050] (1) Weigh 5 parts of ethylene oxide and place them in a sealed jar for later use;

[0051] (2) Add 2 parts of glycolic acid to the autoclave, adjust the pH to 12 using saturated potassium hydroxide solution, and tighten the autoclave to maintain a sealed state.

[0052] (3) Using nitrogen to replace the atmosphere inside the autoclave, and then using nitrogen to press half of the ethylene oxide in the sealed tank into the autoclave. After the addition is completed, stirring for 20 minutes;

[0053] (4) The temperature of the autoclave was raised to 110°C, the stirring speed was set at 300 rpm, the pressure of the autoclave was maintained at 2 MPa, and the remaining ethylene oxide was uniformly pressed into the autoclave using nitrogen pressure for 1 hour;

[0054] (5) After the reaction is completed, the reactor is cooled to 30°C using circulating cold water and the vacuum degree is -0.02 MPa, and the unreacted ethylene oxide in the reaction system is distilled out and recycled;

[0055] (6) The materials inside the reactor are transferred out to obtain small molecule polyether polyols.

[0056] The grinding aid in this embodiment is used in an amount of 0.05-0.15% of the mass of the slag.

[0057] A method for preparing a fine slag powder grinding aid comprises the following steps:

[0058] (1) Preparation of small molecule polyether polyols;

[0059] (2) adding small molecule polyether polyol and water into a stirring kettle and stirring evenly;

[0060] (3) Add the mixture of ethylene glycol and diethylene glycol, sodium cetyl sulfate and water glass to the stirred tank, stir quickly until uniform, then add the defoamer and continue stirring for 30 minutes;

[0061] (4) The material obtained in step (3) is filtered through a 100-mesh cloth to obtain an ultrafine slag powder grinding aid. Example 3

[0062] An ultrafine slag powder grinding aid is prepared from the following raw materials in parts by weight: 30 parts of small molecule polyether polyol, 20 parts of a mixture of ethylene glycol and diethylene glycol, 10 parts of water glass, 0.1 part of sodium hexadecyl sulfonate, 0.1 part of a defoaming agent, and 39.8 parts of water.

[0063] The ethylene glycol and diethylene glycol mixed liquid is a by-product of producing ethylene glycol by ethylene oxide hydration.

[0064] The modulus of the water glass is 3.2.

[0065] The defoaming agent is an organosilicon defoaming agent, model THIX-278, purchased from Yantai Hengxin Chemical Technology Co., Ltd.

[0066] The preparation method of the small molecule polyether polyol is:

[0067] (1) Weigh 6 parts of ethylene oxide and place them in a sealed jar for later use;

[0068] (2) Add 2 parts of glycolic acid to the autoclave, adjust the pH to 12 using saturated potassium hydroxide solution, and tighten the autoclave to maintain a sealed state.

[0069] (3) Using nitrogen to replace the atmosphere inside the autoclave, and then using nitrogen to press half of the ethylene oxide in the sealed tank into the autoclave. After the addition is completed, stirring for 20 minutes;

[0070] (4) The temperature of the autoclave was raised to 120°C, the stirring speed was set at 300 rpm, the pressure of the autoclave was maintained at 2 MPa, and the remaining ethylene oxide was uniformly pressed into the autoclave using nitrogen pressure for 1 hour;

[0071] (5) After the reaction is completed, the reactor is cooled to 30°C using circulating cold water and the vacuum degree is -0.02 MPa, and the unreacted ethylene oxide in the reaction system is distilled out and recycled;

[0072] (6) The materials inside the reactor are transferred out to obtain small molecule polyether polyols.

[0073] The grinding aid in this embodiment is used in an amount of 0.05-0.15% of the mass of the slag.

[0074] A method for preparing a fine slag powder grinding aid comprises the following steps:

[0075] (1) Preparation of small molecule polyether polyols;

[0076] (2) adding small molecule polyether polyol and water into a stirring kettle and stirring evenly;

[0077] (3) Add the mixture of ethylene glycol and diethylene glycol, sodium cetyl sulfate and water glass to the stirred tank, stir quickly until uniform, then add the defoamer and continue stirring for 30 minutes;

[0078] (4) The material obtained in step (3) is filtered through a 100-mesh cloth to obtain an ultrafine slag powder grinding aid. Example 4

[0079] An ultrafine slag powder grinding aid is prepared from the following raw materials in parts by weight: 20 parts of small molecule polyether polyol, 10 parts of a mixture of ethylene glycol and diethylene glycol, 10 parts of water glass, 0.5 parts of sodium hexadecyl sulfonate, 0.5 parts of a defoaming agent, and 20 parts of water.

[0080] The ethylene glycol and diethylene glycol mixed liquid is a by-product of producing ethylene glycol by ethylene oxide hydration.

[0081] The modulus of the water glass is 3.2.

[0082] The defoaming agent is an organosilicon defoaming agent, model THIX-278, purchased from Yantai Hengxin Chemical Technology Co., Ltd.

[0083] The preparation method of the small molecule polyether polyol is:

[0084] (1) Weigh 6 parts of ethylene oxide and place them in a sealed jar for later use;

[0085] (2) Add 2 parts of glycolic acid to the autoclave, adjust the pH to 12 using saturated potassium hydroxide solution, and tighten the autoclave to maintain a sealed state.

[0086] (3) Using nitrogen to replace the atmosphere inside the autoclave, and then using nitrogen to press half of the ethylene oxide in the sealed tank into the autoclave. After the addition is completed, stirring for 20 minutes;

[0087] (4) The temperature of the autoclave was raised to 100°C, the stirring speed was set at 300 rpm, the pressure of the autoclave was maintained at 2 MPa, and the remaining ethylene oxide was uniformly pressed into the autoclave using nitrogen pressure. The reaction time was 1 hour.

[0088] (5) After the reaction is completed, the reactor is cooled to 30°C using circulating cold water and the vacuum degree is -0.02 MPa, and the unreacted ethylene oxide in the reaction system is distilled out and recycled;

[0089] (6) The materials inside the reactor are transferred out to obtain small molecule polyether polyols.

[0090] The grinding aid in this embodiment is used in an amount of 0.05-0.15% of the mass of the slag.

[0091] A method for preparing a fine slag powder grinding aid comprises the following steps:

[0092] (1) Preparation of small molecule polyether polyols;

[0093] (2) adding small molecule polyether polyol and water into a stirring kettle and stirring evenly;

[0094] (3) Add the mixture of ethylene glycol and diethylene glycol, sodium cetyl sulfate and water glass to the stirred tank, stir quickly until uniform, then add the defoamer and continue stirring for 30 minutes;

[0095] (4) The material obtained in step (3) is filtered through a 100-mesh cloth to obtain an ultrafine slag powder grinding aid. Comparative Example 1

[0096] The invention discloses an ultrafine slag powder grinding aid, which is prepared from the following raw materials in parts by weight: 40 parts of diethanol monoisopropanolamine, 15 parts of a mixed solution of ethylene glycol and diethylene glycol, 5 parts of water glass, 0.1 part of sodium hexadecylsulfonate, 0.1 part of a defoaming agent and 39.8 parts of water.

[0097] The ethylene glycol and diethylene glycol mixed liquid is a by-product of producing ethylene glycol by ethylene oxide hydration.

[0098] The modulus of the water glass is 3.2.

[0099] The defoaming agent is an organosilicon defoaming agent, model THIX-278, purchased from Yantai Hengxin Chemical Technology Co., Ltd.

[0100] The grinding aid in this comparative example is used in an amount of 0.05-0.15% of the mass of the slag.

[0101] A method for preparing a fine slag powder grinding aid comprises the following steps:

[0102] (1) Add the alcoholamines, ethylene glycol and diethylene glycol mixture, sodium cetylsulfonate and water into a stirring kettle according to weight and stir evenly;

[0103] (2) Add water glass to the stirring kettle, stir quickly and evenly, then add defoamer and continue stirring for 30 minutes;

[0104] (3) The material obtained in step (2) was filtered through a 100-mesh mesh to obtain the ultrafine slag powder grinding aid described in this comparative example.

[0105] In this comparative example, the small molecule polyether polyol is replaced by diethanol monoisopropanolamine, a common component of the grinding aid, and the remaining raw materials and preparation method are the same as those in Example 1.

[0106] Performance Testing

[0107] In order to further verify the effect of the ultrafine slag powder grinding aid of the present invention, the above Examples 1-4, Comparative Example 1, and a commonly used commercially available slag special grinding aid were added to the slag powder at a dosage of 0.1%, and a blank comparative example was set, i.e., no grinding aid was added; and the various properties thereof were statistically analyzed and compared (data are shown in Table 1 below):

[0108] Experimental Procedure: Seven test groups were divided into each test group. 5 kg of slag was weighed into each test group and added to Examples 1-4, Comparative Example 1, a blank, and a commercially available grinding aid for comparison. The results of the Φ500×500 mm cement experimental small mill with specially formulated steel balls were shown in Table 1.

[0109] Table 1 Performance test results

[0110]

[0111] Example 1 of the present invention, Comparative Example 1, and a commonly used commercially available grinding aid were added to the ultrafine slag powder in a dosage of 0.1% during the grinding process. A blank comparative example was set up, i.e., no grinding aid was added. The various properties of the samples were statistically analyzed and compared (the data are shown in Table 2 below):

[0112] Table 2 Ultrafine mineral powder grinding data

[0113]

[0114] As can be seen from the data in Table 2, the 3d and 28d activity indices of the ultrafine slag powder grinding aid obtained in Example 1 of the present invention are significantly higher than those of the blank example and the commercially available grinding aid group. However, the performance of Comparative Example 1, which does not use a small molecule polyether polyol substance, is weaker than that of the example. It can be seen that the present invention relates to a small molecule polyether polyol, which is crucial for achieving the effect of the grinding aid of the present invention.

[0115] It should be noted that the above embodiments are only some of the preferred embodiments of the present invention, and not all of them. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work should fall within the scope of protection of the present invention.

Claims

1. An ultrafine slag powder grinding aid, characterized in that: The invention is prepared by comprising the following raw materials in parts by weight: 20-40 parts of small molecule polyether polyol, 10-20 parts of a mixture of ethylene glycol and diethylene glycol, 5-10 parts of water glass, 0.1-0.5 parts of sodium hexadecylsulfonate, 0.1-0.5 parts of a defoaming agent and 20-40 parts of water; The preparation method of the small molecule polyether polyol is: (1) Weigh 4-6 parts of ethylene oxide and place them in a sealed jar for later use; (2) Add 2 parts of glycolic acid into the autoclave, adjust the pH to 12 using a saturated potassium hydroxide solution, tighten the autoclave, and maintain the interior of the autoclave in a sealed state; (3) Using nitrogen to replace the atmosphere inside the autoclave, and then using nitrogen to press half of the ethylene oxide in the sealed tank into the autoclave. After the addition is completed, stirring for 20 minutes; (4) Raise the temperature of the autoclave to 100-120°C, stir at 300 rpm, maintain the autoclave pressure at 2 MPa, and begin to uniformly pressurize the remaining ethylene oxide into the autoclave using nitrogen pressure for 1 hour; (5) After the reaction is completed, the autoclave is cooled to 30°C using circulating cold water and the vacuum degree is -0.02 MPa, and the unreacted ethylene oxide in the reaction system is distilled out and recycled; (6) The material inside the high-pressure reactor is transferred out to obtain a small molecule polyether polyol.

2. The ultrafine slag powder grinding aid according to claim 1, characterized in that: The ethylene glycol and diethylene glycol mixed liquid is a by-product of producing ethylene glycol by ethylene oxide hydration.

3. The ultrafine slag powder grinding aid according to claim 1, characterized in that: The modulus of the water glass is 3.

2.

4. The ultrafine slag powder grinding aid according to claim 1, characterized in that: The defoaming agent is an organosilicon defoaming agent.

5. The ultrafine slag powder grinding aid according to claim 1, characterized in that: The dosage of grinding aid is 0.05-0.15% of the slag mass.

6. A method for preparing the ultrafine slag powder grinding aid according to any one of claims 1 to 5, characterized in that: The method comprises the following preparation steps: (1) Preparation of small molecule polyether polyols; (2) adding small molecule polyether polyol and water into a stirring kettle and stirring evenly; (3) Add the mixture of ethylene glycol and diethylene glycol, sodium cetyl sulfate and water glass to the stirred tank, stir quickly until uniform, then add the defoamer and continue stirring for 30 minutes; (4) The material obtained in step (3) is filtered through a 100-mesh cloth to obtain an ultrafine slag powder grinding aid.

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