CN104016613B - A kind ofly improve additive of filling in mine slip degree of mobilization and preparation method thereof - Google Patents

Abstract

The present invention relates to and a kind ofly improve additive of filling in mine slip degree of mobilization and preparation method thereof, be prepared from by following raw materials according by weight percentage: beta-naphthalenesulfonic-acid salt formaldehyde condensation products 35% ~ 45%, polyvinyl alcohol 2% ~ 5%, calglucon 4% ~ 10%, Tai-Ace S 150 1% ~ 2%, citric acid 15% ~ 18%, water 20% ~ 42%.Additive of the present invention can meet mobility and early strength requirement simultaneously, because volume is low, also can reduce the consumption of obturator cement.

Description

An additive for improving the fluidity of mine filling slurry and its preparation method

technical field

The invention relates to a novel additive in mine filling materials, in particular to an additive for improving the fluidity of mine filling slurry.

Background technique

Filling mining technology is more and more widely used in mine mining. In the actual filling process, the filling slurry is transported to the empty area by the pipeline under a certain pump pressure. Due to the bleeding property of the filling slurry, the pumping pipeline is often blocked. It is very important to improve the conveying performance of the filling slurry (increase the fluidity of the slurry). Generally, the main components of filling slurry are tailings or waste rock, cement, and water. In order to improve its fluidity, it is often necessary to adjust the amount of cement and water added. However, in the application process, the influence of the amount of cement and water on the filling strength and fluidity is contradictory.

To meet both strength and fluidity requirements, suitable additives must be added. Because the filling slurry has the characteristics of large volume, low concentration and low cement content. In view of these characteristics of the filling body, the existing additives have the disadvantages of large dosage, high cost, and although the fluidity can be improved, the early strength of the filling slurry is not ideal.

Contents of the invention

The purpose of the present invention is to provide an additive for mine filling slurry that can meet the fluidity and early strength requirements at the same time.

The additive for improving the fluidity of mine filling slurry provided by the present invention is prepared from the following raw materials by weight percentage: 35%~45% of β-naphthalenesulfonate formaldehyde condensate, 2%~5% of polyvinyl alcohol, Calcium gluconate 4%~10%, aluminum sulfate 1%~2%, citric acid 15%~18%, water 20%~42%, total 100%.

The preparation method of above-mentioned additive, comprises the steps:

(1) Add water to the reactor according to the weight percentage, then add β-naphthalenesulfonate formaldehyde condensate, polyvinyl alcohol and calcium gluconate, and stir to react;

(2) Slowly add aluminum sulfate, stir to dissolve and react;

(3) adding citric acid for reaction, and cooling to prepare the additive; the reaction temperature of the steps (1), (2) and (3) is maintained at 80°C to 85°C.

Step (1) Stirring reaction is preferably 20-40 minutes. Step (2) Stir to dissolve, preferably react for 0.8-1.2 hours. The reaction in step (3) is preferably 3 to 5 hours.

The above-mentioned additives are used in improving the fluidity of mine filling slurry, and the added quality of the additives is 0.2%~0.5% of the cement dosage.

β-naphthalene sulfonate formaldehyde condensate is an anionic surfactant. After being added to tailings cement slurry, it can be adsorbed on the surface of cement particles to form a layer of adsorption with hydrophobic groups inward and hydrophilic groups outward. layer, because the hydrophilic group is negatively charged, which is equivalent to the same charge on the surface of each cement particle in the slurry, and the original unstable slurry structure is disintegrated due to the mutual repulsion of the same-sex charges, releasing the wrapped free water, thereby greatly increasing its mobility. Polyvinyl alcohol can prevent the filling slurry from settling and bleeding through bridging. Through the above functions, the conveying performance of the filling slurry can be effectively improved, and the fluidity of the slurry can be improved.

The additive of the present invention is a brown liquid, which is added when preparing the filling slurry, and the added quality is 0.2% to 0.5% of the amount of cement. The specific dosage is determined according to the fluidity increase value of the filling slurry and the strength of the filling body. After using the additive of the invention, the slurry concentration can be increased, the lime-sand ratio can be reduced at the same time, the early strength of the filling body can be improved, and the filling slurry can quickly meet the strength requirement. In addition, due to the low dosage of the additive of the present invention, it can also reduce the amount of cement used in the filling body. It is estimated that cement consumption can be reduced by 60kg per ton of slurry, and the economic benefits are considerable.

detailed description

The β-naphthalenesulfonate formaldehyde condensate (solid) used in the present invention is commercially available, preferably with a weight average molecular weight of 5000-20000; there is no special limitation on the type of the salt, for example, it can be a sodium salt. The present invention has no special requirement on the molecular weight of polyvinyl alcohol, and the range of general molecular weight can be: 110000~130000. The present invention will be described in detail below through specific examples.

Embodiment one

Prepare raw materials by weight percentage: β-naphthalene sulfonate formaldehyde condensate 35%, polyvinyl alcohol 2%, calcium gluconate 5%, aluminum sulfate 1%, citric acid 15%, water 42%; first add water to the reactor , then add β-naphthalenesulfonate formaldehyde condensate, polyvinyl alcohol, and calcium gluconate, keep the temperature at 80°C, stir and react for 30 minutes, slowly add aluminum sulfate and stir to dissolve, react for 1 hour, then add citric acid to react 3 hours, cooling to obtain the additive of the present invention.

The following methods were used to test the performance of the additives prepared in this example, and the results are shown in Table 1 and Table 2.

Fluidity test: Use a cement mortar fluidity tester (model NLD-3) to measure its fluidity. The measurement method is as follows:

1) Put the mixed plastic sand sample into the test mold in two layers, the height of the first layer is 2/3, use a knife to draw 5 times in two directions, and use a knife to draw 10 times evenly and press it 10 times, and the completion Scratch test mold;.

2) Gently lift the test mold vertically, start the jumping table, and complete 30 jumps within 30±1s;

3) After beating, use a caliper to measure the diameter of the bottom surface of the mortar and the diameter perpendicular to it, and calculate the average value as the fluidity of the sample. The test must be completed within 5 minutes. The measurement results are shown in Table 1.

② Compressive strength test:

Use tailing sand and PC32.5 cement, and mix them according to the lime-sand ratio in Table 2. Add different amounts of additives prepared in Example 1 in the slurry according to the mass ratio in Table 2. Stir well and pour them in the 7.07cm×7.07cm×7.07cm triple test mold to ensure that the slurry does not precipitate during the pouring process of the test block, and adopt the pouring method of stirring and injecting mold at the same time. Finally, the 3-day, 7-day, and 28-day strength of the test block was measured with a press, and the uniaxial compressive strength is shown in Table 2.

Table 1 fluidity test results

Table 2 Filling body strength test results

It can be seen from the table that adding this product can greatly improve its fluidity, and can also improve the early strength of the filling body. As a comparison, the inventors also studied the fluidity and strength of the filling body when the additives are β-naphthalene sulfonate formaldehyde condensate and polyvinyl alcohol (mass ratio 35:2). The results are shown in Table 3 and Table 4.

Table 3 fluidity test results

Table 4 Filling body strength test results

From the comparison of Tables 1 to 4, it can be seen that when the additives are β-naphthalenesulfonate formaldehyde condensate and polyvinyl alcohol, although the fluidity of the filling body can be improved, the early strength of the filling body cannot be improved. The invention can achieve the ideal effect of improving both fluidity and early strength.

Embodiment two

Prepare raw materials by weight percentage: β-naphthalene sulfonate formaldehyde condensate 45%, polyvinyl alcohol 5%, calcium gluconate 10%, aluminum sulfate 2%, citric acid 18%, water 20%; Add to the reaction kettle, then add β-naphthalenesulfonate formaldehyde condensate, polyvinyl alcohol, calcium gluconate, keep the temperature at 85°C, stir and react for 30 minutes, slowly add aluminum sulfate and stir to dissolve, react for 1 hour, then add Citric acid was reacted for 5 hours and cooled to obtain the additive of the present invention.

The performance of the additive prepared in this example was tested according to the method of Example 1, and the test results are shown in Table 5 and Table 6.

table 5

Table 6

Claims (7)

1. one kind is improved the additive of filling in mine slip degree of mobilization, it is characterized in that being prepared from by following raw materials according by weight percentage: beta-naphthalenesulfonic-acid salt formaldehyde condensation products 35% ~ 45%, polyvinyl alcohol 2% ~ 5%, calglucon 4% ~ 10%, Tai-Ace S 150 1% ~ 2%, citric acid 15% ~ 18%, water 20% ~ 42%, adds up to 100%; It is prepared from by following step:

(1) according to described weight percent, water is added reactor, then add beta-naphthalenesulfonic-acid salt formaldehyde condensation products, polyvinyl alcohol and calglucon, stirring reaction;

(2) slowly Tai-Ace S 150 is added, stirring and dissolving, reaction;

(3) add citric acid to react, the obtained described additive of cooling;

The reaction of described step (1), (2) and (3) keeps temperature to be 80 DEG C ~ 85 DEG C.

2. additive according to claim 1, is characterized in that the weight-average molecular weight of beta-naphthalenesulfonic-acid salt formaldehyde condensation products is 5000 ~ 20000.

3. a preparation method for additive described in claim 1 or 2, comprises the steps:

(1) according to described weight percent, water is added reactor, then add beta-naphthalenesulfonic-acid salt formaldehyde condensation products, polyvinyl alcohol and calglucon, stirring reaction;

(2) slowly Tai-Ace S 150 is added, stirring and dissolving, reaction;

(3) add citric acid to react, the obtained described additive of cooling;

The reaction of described step (1), (2) and (3) keeps temperature to be 80 DEG C ~ 85 DEG C.

4. preparation method according to claim 3, is characterized in that step (1) stirring reaction 20 ~ 40 minutes.

5. the preparation method according to claim 3 or 4, is characterized in that step (2) stirring and dissolving, reaction 0.8 ~ 1.2 hour.

6. preparation method according to claim 5, is characterized in that step (3) reaction 3 ~ 5 hours.

7. additive described in claim 1 or 2 is improving the application in filling in mine slip degree of mobilization, add that quality is cement consumption 0.2% ~ 0.5% of additive.