High-flow-state slurry / fine silt tailing slurry back-filling early-strength curing agent, preparation method and application

Abstract

The invention relates to the technical field of curing agent preparation, in particular to a high-flow-state slurry / fine silt tailing slurry back-filling early-strength curing agent, a preparation method and application. The mortar comprises the following materials in parts by mass: 5-30 parts of cement, 10-50 parts of water-quenched slag micro powder, 10-30 parts of silicon-calcium slag micro powder, 10-40 parts of industrial waste gypsum, 5-30 parts of gasified slag micro powder, 2-5 parts of an inorganic activator, 5-10 parts of a slurry activator, 0.1-1 part of an accelerator, 0.1-1 part of a water reducing agent and 3-10 parts of modified glass fibers. A large amount of solid waste is used as a main body material, low-carbon development is realized, and meanwhile, the modified glass fiber is added into the material, so that the curing strength of the slurry / fine silt tailing slurry is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of curing agent preparation, and particularly relates to a high-flow-state mud slurry / fine tailing slurry back-filling early-strength curing agent, a preparation method and application. BACKGROUND

[0002] With the continuous acceleration of urbanization construction in China, various types of infrastructure construction are gradually increasing, and a large amount of waste such as mud slurry, slag, residual mud and the like is inevitably generated in the construction process. The engineering waste mud slurry has high water content, large fluidity, small particles and is difficult to separate mud and water, and is one of the most difficult building wastes to handle.

[0003] In recent years, with the decrease of ore grade and the continuous progress of mineral processing technology, more and more fine tailing slurry is generated in the mineral processing process, and the fine tailing slurry has high turbidity, slow natural sedimentation speed and is difficult to handle.

[0004] At present, the treatment methods for waste mud slurry / fine tailing slurry mainly include chemical flocculation precipitation method, high-speed centrifugal dewatering method, solidification treatment method, back-filling recycling method and the like. Among them, the back-filling recycling method has simple process, low equipment requirement and large treatment capacity. An appropriate amount of curing agent is added to the waste mud slurry / fine tailing slurry to form a slurry body with good fluidity, and the slurry body is injected into a tailing pit, a tailing roadway, a foundation pit in a narrow space, a fertilizer groove and the like for back-filling. The mud slurry / fine tailing slurry and the curing agent are chemically reacted to form a consolidated body with certain strength. However, the existing mud slurry / fine tailing slurry curing agent has slow curing speed, low early strength, large dosage and high cost, which limits the application field and application scale of the curing agent. Therefore, it is urgent to develop a curing material with fast curing speed, high early strength, small dosage and low price, so as to rapidly solidify the mud slurry / fine tailing slurry and improve the resource utilization efficiency of the mud slurry / fine tailing slurry. SUMMARY

[0005] The present application aims to provide a high-flow-state mud slurry / fine tailing slurry back-filling early-strength curing agent, a preparation method and application, so as to solve the problems in the background.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical scheme. A high-flow-state mud slurry / fine tailing slurry back-filling early-strength curing agent includes the following components by mass fraction: cement 5-30 parts, water-quenched slag micro powder 10-50 parts, silicon-calcium slag micro powder 10-30 parts, industrial waste gypsum 10-40 parts, gasification slag micro powder 5-30 parts, inorganic activator 2-5 parts, mud activator 5-10 parts, accelerator 0.1-1 part, water reducing agent 0.1-1 part and modified glass fiber 3-10 parts; The preparation method of the modified glass fiber includes the following steps: S101, completely immerse the nanometer silicon dioxide in the silane coupling agent solution for 5-60 min, then add the surface roughened glass fiber, ultrasonic treatment for 10-60 min, then filter, the filtered product is washed with sufficient deionized water and then dried to obtain the pretreated glass fiber; S102, immerse the pretreated glass fiber obtained in step S101 in the immersion solution for immersion treatment, immerse for 1-3 h, then take out the immersed pretreated glass fiber, and vacuum dry at 40-50℃ to constant weight to obtain the modified glass fiber; The immersion solution comprises acrylic acid, cellulose ether, polyacrylamide and deionized water; The mass ratio between the cellulose ether, the acrylic acid, the polyacrylamide and the deionized water is 1:(3-8):(0.5-2):(40-80).

[0007] Further, the concentration of the silane coupling agent in step S101 is 5-10wt%, the solvent used in the silane coupling agent solution is ethylene glycol, and the silane coupling agent is KH550.

[0008] Further, the mass ratio between the nanometer silicon dioxide, the surface roughened glass fiber and the ethylene glycol in step S101 is 1:(2-4):(20-30).

[0009] Further, the specific treatment steps of the surface roughened glass fiber in step S101 are as follows: Completely immerse the glass fiber in the ethanol solution of tetramethylammonium hydroxide for 1.5h.

[0010] Further, the concentration of the tetramethylammonium hydroxide is 1wt%; microwave treatment is carried out simultaneously during the immersion treatment of the glass fiber in the ethanol of tetramethylammonium hydroxide, and the power of the microwave is 600W.

[0011] Further, the cellulose ether in step S102 is specifically selected as hydroxypropyl methyl cellulose.

[0012] Further, the accelerator is one of sodium silicate, calcium formate, lithium carbonate and sodium carbonate; the water reducing agent is one of polycarboxylate water reducing agent, polyacrylate water reducing agent, naphthalene series water reducing agent and aliphatic water reducing agent; the inorganic activator is one of calcium carbide slag powder, saponification waste slag powder and caustic mud powder; and the mud activator is one of marble waste slag powder and waste stone powder.

[0013] A preparation method of a high-flow-state mud / fine mud tailing slurry backfilling early-strength solidifying agent, comprising the following steps: S1, the cement, inorganic activator, mud activator, accelerator, water reducing agent are weighed according to the proportion, and are stirred in a mixer for 5-15 min to prepare a premix; S2, the water-quenched slag powder, silicon-calcium slag powder, industrial byproduct waste gypsum, gasification slag powder and modified glass fiber are added to the premix prepared in step S1 according to the mass fraction, and stirring is continued for 10-30 min to prepare a back-filling early-strength solidifying agent.

[0014] The application of a high-flow-state mud / fine mud tailings back-filling early-strength solidifying agent in solidifying high-flow-state mud / fine mud tailings.

[0015] Compared with the prior art, the application has the beneficial effects that: 1. In the application, the solidifying agent is prepared from a large amount of solid waste, which effectively saves resources and is suitable for low-carbon development concept. 2. In the application, the surface-roughened glass fiber is suitable for loading nano-silicon dioxide, and the glass fiber is immersed in a mixed solution of cellulose ether, acrylic acid, polyacrylamide and deionized water to form a film structure on the surface of the glass fiber, preventing the nano-silicon dioxide from falling off the surface of the glass fiber during stirring. BRIEF DESCRIPTION OF DRAWINGS

[0016] Fig. 1 The process flow chart of the application is shown in the figure. Fig. 2 The process flow chart of the preparation of the modified glass fiber of the application is shown in the figure. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the application will be described clearly and completely below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0018] Please refer to Figs. 1-2 The application provides: Embodiment 1 A preparation method of a high-flow-state mud / fine mud tailings back-filling early-strength solidifying agent comprises the following steps: S1, take 15 parts of cement, 4 parts of inorganic activator, 8 parts of mud activator, 0.4 parts of accelerator and 0.2 parts of water reducing agent, inorganic activator is calcium carbide slag powder, mud activator is marble waste residue powder, accelerator is sodium silicate, water reducing agent is polycarboxylate water reducing agent, stir in the blender for 10 min, stirring speed is 150 rpm, prepare premix; S2, add 20 parts of water quenched slag powder, 18 parts of silicon calcium slag powder, 30 parts of industrial waste gypsum, 15 parts of gasification slag powder and modified glass fiber 7 parts to the premix prepared in step S1, continue to stir for 20 min, stirring speed is 200 rpm, prepare back filling early strength solidifying agent; The preparation method of the modified glass fiber comprises the following steps: S101, immerse 4 parts of nano silicon dioxide in the silane coupling agent solution for 30 min, the concentration of the silane coupling agent is 8 wt%, the solvent used in the silane coupling agent solution is ethylene glycol, the amount of ethylene glycol used is 95 parts, the silane coupling agent is KH550, then add 12 parts of surface rough glass fiber, ultrasonic treatment for 40 min, ultrasonic frequency is 20 kHz, then filter, the filtered product is washed with sufficient deionized water and then dried to obtain pretreated glass fiber; S102, put the pretreated glass fiber obtained in step S101 into the immersion liquid for immersion treatment, take out the pretreated glass fiber after immersion for 2 h, and vacuum dry at 45℃ to constant weight to obtain modified glass fiber; The immersion liquid comprises acrylic acid, cellulose ether, polyacrylamide and deionized water, the mass ratio between the cellulose ether, acrylic acid, polyacrylamide and deionized water is 1:3:0.5:40, and the total mass of the immersion liquid is 5 times the mass of the pretreated glass fiber added in step S102.

[0019] Example 2 A preparation method of a high flow state mud / fine mud tailing slurry back filling early strength solidifying agent, comprising the following steps: S1, take 5 parts of cement, 2 parts of inorganic activator, 5 parts of mud activator, 0.1 parts of accelerator and 0.1 parts of water reducing agent, accelerator is calcium formate, water reducing agent is polyacrylate water reducing agent, inorganic activator is saponified waste residue powder, mud activator is waste stone powder, stir in the blender for 5 min, stirring speed is 150 rpm, prepare premix; S2, add 10 parts of water quenched slag powder, 10 parts of silicon calcium slag powder, 10 parts of industrial waste gypsum, 5 parts of gasification slag powder and modified glass fiber 3 parts to the premix prepared in step S1, continue to stir for 10 min, stirring speed is 200 rpm, prepare back filling early strength solidifying agent.

[0020] The preparation method of the modified glass fiber comprises the following steps: S101, 2.5 parts of nanometer silicon dioxide were completely immersed in a silane coupling agent solution for 5 min, the concentration of the silane coupling agent was 5 wt%, the solvent used in the silane coupling agent solution was ethylene glycol, the amount of ethylene glycol was 50 parts, the silane coupling agent was KH550, then 5 parts of surface roughened glass fiber was added, ultrasonic treatment was performed for 10 min, the ultrasonic frequency was 20 kHz, then filtration was performed, the filtration product was washed with sufficient deionized water and then dried to obtain pretreated glass fiber; S102, the pretreated glass fiber obtained in step S101 was placed in an immersion solution for immersion treatment, after immersion for 1 h, the pretreated glass fiber after immersion was taken out and vacuum dried at 40°C to constant weight to obtain modified glass fiber; The immersion solution comprises acrylic acid, cellulose ether, polyacrylamide and deionized water, the mass ratio between the cellulose ether, the acrylic acid, the polyacrylamide and the deionized water is 1:8:2:80, and the total mass of the immersion solution is 5 times the mass of the pretreated glass fiber added in step S102.

[0021] Example 3 A preparation method of a high-flow-state mud / fine mud tailing pulp backfill early strength solidifying agent, comprising the following steps: S1, 30 parts of cement, 5 parts of inorganic activator, 10 parts of mud activator, 1 part of accelerator and 1 part of water reducing agent were taken, the accelerator was lithium carbonate, the water reducing agent was naphthalene water reducing agent, the inorganic activator was caustic mud powder, and the mud activator was marble waste residue powder, which was stirred in a stirrer for 15 min at a stirring speed of 150 rpm to prepare a premix; S2, 50 parts of water-quenched slag powder, 30 parts of silicon-calcium slag powder, 40 parts of industrial waste gypsum, 30 parts of gasification slag powder and modified glass fiber 10 parts were added to the premix prepared in step S1, and stirring was continued for 30 min at a stirring speed of 200 rpm to prepare a backfill early strength solidifying agent; The preparation method of the modified glass fiber comprises the following steps: S101, 3 parts of nanometer silicon dioxide treated in step S101 were completely immersed in a silane coupling agent solution for 60 min, the concentration of the silane coupling agent was 10 wt%, the solvent used in the silane coupling agent solution was ethylene glycol, the amount of ethylene glycol was 90 parts, the silane coupling agent was KH550, then 12 parts of surface roughened glass fiber was added, ultrasonic treatment was performed for 60 min, the ultrasonic frequency was 20 kHz, then filtration was performed, the filtration product was washed with sufficient deionized water and then dried to obtain pretreated glass fiber; S102, the pretreated glass fiber obtained in step S101 was placed in an immersion solution for immersion treatment, after immersion for 3 h, the pretreated glass fiber after immersion was taken out and vacuum dried at 50°C to constant weight to obtain modified glass fiber; The impregnation solution includes acrylic acid, cellulose ether, polyacrylamide and deionized water, the mass ratio between the cellulose ether, acrylic acid, polyacrylamide and deionized water is 1:5:1:60, and the total mass of the impregnation solution is 5 times the mass of the pretreated glass fiber added in step S102.

[0022] Embodiment 4 A preparation method of a high-flow-state mud / fine mud tailing pulp backfill early strength solidifying agent, comprising the following steps: S1, take 22 parts of cement, 5 parts of inorganic activator, 8 parts of mud activator, 0.6 parts of accelerator and 0.5 parts of water reducing agent, the accelerator is sodium carbonate, the water reducing agent is aliphatic retarder, the inorganic activator is calcium carbide slag powder, and the mud activator is marble waste residue powder, and the pre-mixed material is prepared by stirring in a stirrer for 12 min at a stirring speed of 150 rpm; S2, add 40 parts of water-quenched slag powder, 20 parts of silicon-calcium slag powder, 25 parts of industrial waste gypsum, 15 parts of gasification slag powder and 8 parts of modified glass fiber to the pre-mixed material prepared in step S1, and continue to stir for 20 min at a stirring speed of 200 rpm to prepare the backfill early strength solidifying agent.

[0023] The preparation method of the modified glass fiber comprises the following steps: S101, immerse 4 parts of nano silicon dioxide in a silane coupling agent solution for 50 min, the concentration of the silane coupling agent is 8 wt%, the solvent used in the silane coupling agent solution is ethylene glycol, the amount of ethylene glycol used is 110 parts, the silane coupling agent is KH550, then 12 parts of surface roughened glass fiber is added, ultrasonic treatment is performed for 50 min at a frequency of 20 kHz, then filtration is performed, the filtration product is washed with sufficient deionized water and then dried to obtain pretreated glass fiber; S102, put the pretreated glass fiber obtained in step S101 into an impregnation solution for impregnation treatment, take out the impregnated pretreated glass fiber after impregnation for 1-3 h, and vacuum dry at 40-50℃ to constant weight to obtain modified glass fiber; The impregnation solution includes acrylic acid, cellulose ether, polyacrylamide and deionized water, the mass ratio between the cellulose ether, acrylic acid, polyacrylamide and deionized water is 1:6:1.2:50, and the total mass of the impregnation solution is 5 times the mass of the pretreated glass fiber added in step S102.

[0024] The cellulose ether is specifically selected as hydroxypropyl methyl cellulose in the above embodiment.

[0025] The average particle size of the nano silicon dioxide used in the above embodiment is 20 nm.

[0026] The specific treatment steps of the surface-roughened glass fiber in step S102 in the above embodiment are as follows: The glass fiber was completely immersed in the ethanol solution of tetramethylammonium hydroxide for 1.5 h, and the concentration of the tetramethylammonium hydroxide was 1 wt%; during the immersion treatment of the glass fiber in the ethanol solution of tetramethylammonium hydroxide, microwave treatment was simultaneously performed, and the power of the microwave was 600 W.

[0027] The water-quenched slag in the above embodiment is a product obtained by subjecting the solid waste slag generated in the blast furnace ironmaking process to water quenching and rapid cooling treatment, and the main components include calcium oxide, silicon dioxide and aluminum oxide, wherein the content of CaO is 35-50%, the content of SiO2 is 30-40%, and the content of Al2O3 is 5-20%; The silica-calcium slag powder in the above embodiment is a solid residue remaining after the alkali and limestone are added to the fly ash for sintering, and then alumina is extracted by a wet method, and the alkali is recovered; because it mainly contains two elements of silica and calcium, it is called silica-calcium slag; the silica-calcium slag is a beige powdery substance, which is loose and porous, and has a bulk density of 1.20-1.50 g / cm 3 After the alkali is removed, it is a white powdery substance, and can be pressure-cast into a block-shaped object with certain strength; the chemical components thereof include CaO, SiO2, Al2O3, Fe2O3, MgO, TiO2, Na2O, K2O and H2O; the content of CaO is 30-50%, the content of SiO2 is 30-40%, and the content of Al2O3 is 5-15%; The gasification slag powder in the above embodiment is a solid waste generated in the coal gasification process, which is mainly divided into coarse slag and fine slag; the content of SiO2 is 30%-60%, the content of CaO is 10-30%, and the content of Al2O3 is 5-15%; The marble waste slag powder in the above embodiment is mainly derived from the granular waste generated in the processing of marble, including grinding and cutting, and the chemical components thereof are mainly calcium carbonate, which is similar to the original marble. The waste stone powder in the above embodiment refers to the fine particles with a particle size of less than 0.16 mm generated in the stone processing process, which is mainly derived from cutting, sawing and polishing processes, and is divided into marble powder (mainly carbonate minerals) and granite powder (mainly silicate minerals) according to different components.

[0028] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that step S102 is cancelled, and the remaining steps are completely the same as those in Example 1.

[0029] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the addition of the modified glass fiber is cancelled in step S2, and 1.75 parts of nano-silicon dioxide and 5.25 parts of surface-roughened glass fiber are added instead, and the remaining steps are completely the same as those in Example 1.

[0030] Comparative Example 3 Comparative Example 3 is different from Example 1 in that the surface roughened glass fiber added in step S101 is replaced by common glass fiber, and the rest of the steps are exactly the same as Example 1.

[0031] The backfill early strength curing agent prepared in Examples 1-4 and Comparative Examples 1-3 According to the mass ratio of absolute dry soil (fine mud tailings) : water 4:1, an appropriate amount of slurry / fine mud tailings slurry (soil / fine mud tailings) and water is weighed, and it is quickly stirred in a blender for 15 min to prepare a high-fluidity slurry / fine mud tailings slurry; The backfill early strength curing agent is added to the high-fluidity slurry / fine mud tailings slurry prepared in step 1) at 3%~200% of the weight of the high-fluidity slurry / fine mud tailings slurry, and is quickly stirred for 20 min to prepare a high-fluidity early strength slurry / fine mud tailings slurry; The above high-fluidity early strength slurry / fine mud tailings slurry is injected into a mold for curing and solidification, the slurry / fine mud tailings slurry is 12h initial setting, and the 3d and 28d compressive strengths of the slurry / fine mud tailings slurry are measured, and the measurement results are shown in Table 1 below: Table 1: 3d and 28d compressive strength test table of the curing agent prepared in Examples 1-4 and Comparative Examples 1-3 applied to the high-fluidity slurry / fine mud tailings slurry after curing:

[0032] From the data of Example 1 and Comparative Example 1 in Table 1 above, it can be seen that after the pre-treatment of the glass fiber in the immersion liquid is cancelled in the present application, the strength decreases; from the data of Example 1 and Comparative Example 2, it can be seen that the glass fiber and nano-silica are added separately to the slurry, and the strength decreases; from the data of Example 1 and Comparative Example 3, it can be seen that after the surface roughening treatment of the glass fiber is cancelled, the strength also decreases.

[0033] Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A high-fluidity mud / fine mud tailings slurry backfill early-strength solidification agent, characterized in that, Materials comprising the following components by weight: 5-30 parts cement, 10-50 parts water-quenched slag powder, 10-30 parts calcium silicate slag powder, 10-40 parts industrial waste gypsum, 5-30 parts gasification slag powder, 2-5 parts inorganic activator, 5-10 parts mud activator, 0.1-1 part quick-setting agent, 0.1-1 part water-reducing agent, and 3-10 parts modified glass fiber; The method for preparing the modified glass fiber includes the following steps: S101. The nano-silica is completely immersed in a silane coupling agent solution for 5-60 minutes. Then, rough glass fiber is added and ultrasonically treated for 10-60 minutes. After filtration, the filtered product is washed with sufficient deionized water and then dried to obtain pretreated glass fiber. S102. The pretreated glass fiber obtained in step S101 is immersed in the impregnation solution for 1-3 hours. After immersion, the pretreated glass fiber is taken out and vacuum dried at 40-50°C to constant weight to obtain modified glass fiber. The impregnation solution includes acrylic acid, cellulose ether, polyacrylamide, and deionized water; The mass ratio of cellulose ether, acrylic acid, polyacrylamide and deionized water is 1:(3-8):(0.5-2):(40-80).

2. The high-fluidity mud / fine mud tailings slurry backfilling early-strength solidification agent according to claim 1, characterized in that, In step S101, the concentration of the silane coupling agent is 5-10 wt%, the solvent used in the silane coupling agent solution is ethylene glycol, and the silane coupling agent is KH550.

3. The high-fluidity mud / fine mud tailings slurry backfilling early-strength solidification agent according to claim 1, characterized in that, In step S101, the mass ratio of nano-silica, rough-surfaced glass fiber, and ethylene glycol is 1:(2-4):(20-30).

4. The high-fluidity mud / fine mud tailings slurry backfilling early-strength solidification agent according to claim 1, characterized in that, The specific steps for treating the roughened glass fiber in step S101 are as follows: The glass fiber was completely immersed in an ethanol solution of tetramethylammonium hydroxide for 1.5 hours.

5. The high-fluidity mud / fine mud tailings slurry backfilling early-strength solidification agent according to claim 4, characterized in that, The concentration of the tetramethylammonium hydroxide is 1 wt%; during the impregnation process of the glass fiber in the ethanol of tetramethylammonium hydroxide, it is simultaneously subjected to microwave treatment with a microwave power of 600W.

6. The high-fluidity mud / fine mud tailings slurry backfilling early-strength solidification agent according to claim 1, characterized in that, The cellulose ether in step S102 is specifically selected as hydroxypropyl methylcellulose.

7. The high-fluidity mud / fine mud tailings slurry backfilling early-strength solidification agent according to claim 1, characterized in that, The quick-setting agent is one of sodium silicate, calcium formate, lithium carbonate, and sodium carbonate; the water-reducing agent is one of polycarboxylate water-reducing agent, polyacrylate water-reducing agent, naphthalene-based water-reducing agent, and aliphatic slowing agent; the inorganic activator is one of carbide slag powder, saponification waste powder, and causticized mud powder; and the mud activator is one of marble waste powder and waste stone powder.

8. The method for preparing the high-fluidity mud / fine mud tailings slurry backfill early-strength solidification agent according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Weigh out cement, inorganic activator, mud activator, quick-setting agent and water-reducing agent according to the proportion, and mix them in a mixer for 5-15 minutes to obtain a premix. S2. Add water-quenched slag powder, calcium silicate slag powder, industrial by-product waste gypsum, gasification slag powder and modified glass fiber to the premix obtained in step S1 according to the mass parts, and continue stirring for 10-30 minutes to obtain the refilling early strength curing agent.

9. The application of the high fluidity mud / fine mud tailings slurry backfill early strength solidifier as described in any one of claims 1-7 in the solidification of high fluidity mud / fine mud tailings slurry.

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