High-flow-state mud / fine mud tailing pulp filling early-strength solidifying agent, preparation method and application

Abstract

The application relates to the technical field of curing agent preparation, in particular to a high-flow-state mud / fine-mud tailing slurry back-filling early-strength curing agent, a preparation method and application. The material comprises the following components in parts by mass: 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, quick coagulant 0.1-1 part, water reducing agent 0.1-1 part and modified glass fiber 3-10 parts. A large amount of solid waste is used as the main material, low-carbon development is realized, and the modified glass fiber is added in the material, so that the curing strength of the mud / fine-mud tailing slurry is improved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of curing agent preparation, in particular to a high-flow-state mud slurry / fine mud 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 mud, slag, residual mud and other waste is inevitably generated in the construction process. The engineering waste mud 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 mud tailing slurry is generated in the mineral processing process, and the fine mud tailing slurry has the characteristics of high turbidity, slow natural sedimentation speed and difficult treatment.

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

[0005] The application aims to provide a high-flow-state mud slurry / fine mud 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 application provides the following technical scheme:

[0007] A high-flow-state mud slurry / fine mud tailing slurry back-filling early-strength curing agent comprises the following components by mass fraction:

[0008] 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, accelerating agent 0.1-1 part, water reducing agent 0.1-1 part and modified glass fiber 3-10 parts;

[0009] The preparation method of the modified glass fiber comprises the following steps:

[0010] 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, wash the filtered product with sufficient deionized water, and dry to obtain the pretreated glass fiber;

[0011] S102, immerse the pretreated glass fiber obtained in step S101 in the immersion solution for immersion treatment, take out the immersed pretreated glass fiber after 1-3 h, and vacuum dry at 40-50℃ to constant weight to obtain the modified glass fiber;

[0012] The immersion solution comprises acrylic acid, cellulose ether, polyacrylamide and deionized water;

[0013] The mass ratio among the cellulose ether, the acrylic acid, the polyacrylamide and the deionized water is 1:(3-8):(0.5-2):(40-80).

[0014] 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.

[0015] Further, the mass ratio among the nanometer silicon dioxide, the surface roughened glass fiber and the ethylene glycol in step S101 is 1:(2-4):(20-30).

[0016] Further, the specific treatment steps of the surface roughened glass fiber in step S101 are as follows:

[0017] Completely immerse the glass fiber in the ethanol solution of tetramethylammonium hydroxide for 1.5h.

[0018] 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.

[0019] Further, the cellulose ether in step S102 is specifically selected as hydroxypropyl methyl cellulose.

[0020] 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.

[0021] A preparation method of a high-flow-state mud / fine mud tailing pulp back-filling early strength solidifying agent, comprising the following steps:

[0022] S1, the cement, inorganic activator, mud activator, accelerator, water reducing agent are weighed according to the proportion, and are stirred in a stirrer for 5-15 min to prepare a premix;

[0023] S2, the water-quenched slag powder, silicon-calcium slag powder, industrial by-product waste gypsum, gasification slag powder and modified glass fiber are added to the premix prepared in step S1 according to the mass fraction, and the stirring is continued for 10-30 min to prepare the back-filling early strength solidifying agent.

[0024] The application of a high-flow-state mud / fine mud tailing pulp back-filling early strength solidifying agent in solidifying high-flow-state mud / fine mud tailing pulp.

[0025] Compared with the prior art, the present application has the beneficial effects that:

[0026] 1. In the present 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. Meanwhile, the modified glass fiber is added in the present application, and the nano-sized silicon dioxide loaded on the modified glass fiber is evenly dispersed in the slurry.

[0027] 2. In the present application, the glass fiber with rough surface is suitable for loading nano-sized silicon dioxide. Meanwhile, 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, which prevents the nano-sized silicon dioxide from falling off the surface of the glass fiber during stirring. In the solidification process, the film structure gradually disappears, the contact between the silicon dioxide and the slurry increases, the strength is improved, and the cellulose ether and polyacrylamide as viscosity materials are beneficial to the improvement of the solidification strength of the mud / fine mud tailing pulp. BRIEF DESCRIPTION OF DRAWINGS

[0028] Fig. 1 The process flow chart of the present application is shown in the figure;

[0029] Fig. 2 The process flow chart of the preparation of the modified glass fiber of the present application is shown in the figure. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0031] Please refer toFigs. 1-2 The present application provides:

[0032] Embodiment 1

[0033] A preparation method of a high-flow-state mud / fine mud tailings backfill early strength solidifying agent, comprising the following steps:

[0034] 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, the inorganic activator is calcium carbide slag powder, the mud activator is marble waste residue powder, the accelerator is sodium silicate, and the water reducing agent is polycarboxylate water reducing agent, and the premix is prepared by stirring in a stirrer for 10 min at a stirring speed of 150 rpm;

[0035] 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 7 parts of modified glass fiber to the premix prepared in step S1, and continue to stir for 20 min at a stirring speed of 200 rpm to prepare a backfill early strength solidifying agent;

[0036] The preparation method of the modified glass fiber comprises the following steps:

[0037] S101, immerse 4 parts of nano silicon dioxide in a 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 12 parts of glass fiber with rough surface are added, ultrasonic treatment is performed for 40 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;

[0038] S102, the pretreated glass fiber obtained in step S101 is immersed in an immersion liquid for immersion treatment, after 2h of immersion, the immersed pretreated glass fiber is taken out and vacuum dried at 45°C to constant weight to obtain modified glass fiber;

[0039] The immersion liquid comprises acrylic acid, cellulose ether, polyacrylamide and deionized water, and the mass ratio among the cellulose ether, the acrylic acid, the polyacrylamide and the 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.

[0040] Embodiment 2

[0041] A preparation method of a high-flow-state mud / fine mud tailings backfill early strength solidifying agent, comprising the following steps:

[0042] 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, the accelerator is calcium formate, the water reducing agent is polyacrylate water reducing agent, the inorganic activator is saponified waste residue powder, and the mud activator is waste stone powder, which is stirred in a blender for 5 min at a stirring speed of 150 rpm to prepare a premix;

[0043] 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 3 parts of modified glass fiber to the premix prepared in step S1, continue to stir for 10 min at a stirring speed of 200 rpm to prepare a backfill early strength curing agent.

[0044] The preparation method of the modified glass fiber comprises the following steps:

[0045] S101, immerse 2.5 parts of nano silicon dioxide in a silane coupling agent solution for 5 min, the concentration of the silane coupling agent is 5 wt%, the solvent used in the silane coupling agent solution is ethylene glycol, the amount of ethylene glycol is 50 parts, the silane coupling agent is KH550, then add 5 parts of surface roughened glass fiber, ultrasonic treatment for 10 min at a frequency of 20 kHz, then filter, the filtered product is washed with sufficient deionized water and then dried to obtain pretreated glass fiber;

[0046] S102, put the pretreated glass fiber obtained in step S101 into the dipping solution for dipping treatment, take out the dipped pretreated glass fiber after dipping for 1 h, and vacuum dry at 40℃ to constant weight to obtain modified glass fiber;

[0047] The dipping solution comprises acrylic acid, cellulose ether, polyacrylamide and deionized water, and the mass ratio of cellulose ether, acrylic acid, polyacrylamide and deionized water is 1:8:2:80, and the total mass of the dipping solution is 5 times the mass of the pretreated glass fiber added in step S102.

[0048] Example 3

[0049] A preparation method of a high-flow-state mud / fine mud tailings backfill early strength curing agent, comprising the following steps:

[0050] S1, take 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, the accelerator is lithium carbonate, the water reducing agent is naphthalene water reducing agent, the inorganic activator is caustic mud powder, and the mud activator is marble waste residue powder, which is stirred in a blender for 15 min at a stirring speed of 150 rpm to prepare a premix;

[0051] 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 10 parts of modified glass fiber are added to the premix prepared in step S1, and stirring is continued for 30 min at a stirring speed of 200 rpm to prepare a backfill early strength curing agent;

[0052] The preparation method of the modified glass fiber comprises the following steps:

[0053] S101, 3 parts of nano-silicon dioxide treated in step S101 are completely immersed in a silane coupling agent solution for 60 min, the concentration of the silane coupling agent is 10 wt%, the solvent used in the silane coupling agent solution is ethylene glycol, the amount of ethylene glycol used is 90 parts, the silane coupling agent is KH550, then 12 parts of surface roughened glass fiber is added, ultrasonic treatment is performed for 60 min at an ultrasonic frequency of 20 kHz, then filtration is performed, the filtered product is washed with sufficient deionized water and then dried to obtain pretreated glass fiber;

[0054] S102, the pretreated glass fiber obtained in step S101 is placed in an impregnation solution for impregnation treatment, after impregnation for 3 h, the impregnated pretreated glass fiber is taken out and vacuum dried at 50°C to constant weight to obtain modified glass fiber;

[0055] The impregnation 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 1:5:1:60, and the total mass of the impregnation solution is 5 times the mass of the pretreated glass fiber added in step S102.

[0056] Example 4

[0057] A preparation method of a high-flow-state mud / fine mud tailings backfill early strength curing agent, comprising the following steps:

[0058] S1, 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 are taken, the accelerator is sodium carbonate, the water reducing agent is an aliphatic retarder, the inorganic activator is carbide slag powder, and the mud activator is marble waste slag powder, which is stirred in a stirrer for 12 min at a stirring speed of 150 rpm to prepare a premix;

[0059] S2, 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 are added to the premix prepared in step S1, and stirring is continued for 20 min at a stirring speed of 200 rpm to prepare a backfill early strength curing agent.

[0060] The preparation method of the modified glass fiber comprises the following steps:

[0061] S101. Four parts of nano-silica were completely impregnated in a silane coupling agent solution for 50 minutes. The concentration of the silane coupling agent was 8 wt%. The solvent used in the silane coupling agent solution was ethylene glycol, and the amount of ethylene glycol was 110 parts. The silane coupling agent was KH550. Then, 12 parts of rough-surfaced glass fiber were added, and the mixture was ultrasonically treated for 50 minutes at a frequency of 20 kHz. After filtration, the filtered product was washed with sufficient deionized water and then dried to obtain pretreated glass fiber.

[0062] 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.

[0063] 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 1:6:1.2:50. The total mass of the impregnation solution is 5 times the mass of the pretreated glass fiber added in step S102.

[0064] In the above embodiments, the cellulose ether was specifically selected as hydroxypropyl methylcellulose.

[0065] The average particle size of the nano-silica used in the above embodiments is 20 nm.

[0066] The specific processing steps for the roughened glass fiber in step S102 of the above embodiment are as follows:

[0067] The glass fiber was completely impregnated in an ethanol solution of tetramethylammonium hydroxide for 1.5 hours. The concentration of tetramethylammonium hydroxide was 1 wt%. During the impregnation process of the glass fiber in the ethanol solution of tetramethylammonium hydroxide, it was simultaneously subjected to microwave treatment with a power of 600 W.

[0068] In the above embodiments, the water-quenched slag is a product of solid waste slag generated during blast furnace ironmaking after water quenching and rapid cooling. Its main components include calcium oxide, silicon dioxide and aluminum oxide, with CaO content of 35-50%, SiO2 content of 30-40%, and Al2O3 content of 5-20%.

[0069] In the above embodiments, the silica-calcium slag powder is produced by adding alkali and limestone to fly ash, sintering it, and then extracting alumina using a wet process. The solid residue remaining after recovering the alkali is called silica-calcium slag because it mainly contains silicon and calcium. Silica-calcium slag is a light yellow powder, loose and porous, with a bulk density of 1.20-1.5 g / cm³. 3, and after dealkalization, it is white powder and can be pressure-cast into a block with certain strength, and its chemical composition is composed of CaO, SiO2, Al2O3, Fe2O3, MgO, TiO2, Na2O, K2O and H2O, etc.; the content of CaO is 30-50%, the content of SiO2 is 30-40%, and the content of Al2O3 is 5-15%;

[0070] In the above embodiment, the gasification slag powder is a solid waste produced in the process of coal gasification, 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%;

[0071] In the above embodiment, the marble waste slag powder is mainly granular waste produced in the process of marble processing, including grinding, cutting and other links, and its chemical composition is mainly calcium carbonate, similar to the marble raw stone;

[0072] In the above embodiment, the waste stone powder refers to a fine particle with a particle size of less than 0.16 mm produced in the process of stone processing, mainly 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.

[0073] Comparative Example 1

[0074] Comparative Example 1 is different from Example 1 in that step S102 is cancelled, and the remaining steps are completely the same as Example 1.

[0075] Comparative Example 2

[0076] Comparative Example 2 is different from Example 1 in that the addition of modified glass fiber is cancelled in step S2, and 1.75 parts of nano silicon dioxide and 5.25 parts of surface rough glass fiber are added instead, and the remaining steps are completely the same as Example 1.

[0077] Comparative Example 3

[0078] Comparative Example 3 is different from Example 1 in that the surface rough glass fiber added in step S101 is changed to ordinary glass fiber, and the remaining steps are completely the same as Example 1.

[0079] The backfilling early strength solidifying agent prepared in Examples 1-4 and Comparative Examples 1-3

[0080] According to the mass ratio of absolute dry soil (fine mud tailings) : water 4:1, an appropriate amount of mud slurry / fine mud tailings slurry (soil / fine mud tailings) and water are weighed, and they are quickly stirred in a stirrer for 15 min to prepare a high-flow mud slurry / fine mud tailings slurry;

[0081] The backfill early strength curing agent is added to the high-fluidity slurry / fine slurry tailing slurry prepared in step 1) in an amount of 3% to 200% by weight of the high-fluidity slurry / fine slurry tailing slurry, and is rapidly stirred for 20 min to prepare a high-fluidity early strength slurry / fine slurry tailing slurry;

[0082] The high-fluidity early strength slurry / fine slurry tailing slurry prepared above is injected into a mold for curing and solidification, 12h initial setting of the slurry / fine slurry tailing slurry is achieved, and the 3d and 28d compressive strengths of the slurry / fine slurry tailing slurry are determined, and the determination results are shown in Table 1 below:

[0083] Table 1: 3d and 28d compressive strength test table of the cured agent prepared in Examples 1-4 and Comparative Examples 1-3 after being applied to the high-fluidity slurry / fine slurry tailing slurry for curing:

[0084]

[0085] As can be seen from the data of Example 1 and Comparative Example 1 in Table 1 above, the strength decreases after the pre-treatment of soaking the glass fiber in the impregnating liquid is cancelled in the present application; as can be seen from the data of Example 1 and Comparative Example 2, the strength decreases when the glass fiber and nano-silica are added separately to the slurry; as can be seen from the data of Example 1 and Comparative Example 3, the strength also decreases after the roughening treatment of the surface of the glass fiber is cancelled.

[0086] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A high flow state mud / fine tailings slurry backfill early strength solidifying agent, characterized by, The material comprises the following components by mass fraction: cement 5-30 parts, water-granulated slag powder 10-50 parts, silicon-calcium slag powder 10-30 parts, industrial waste gypsum 10-40 parts, gasification slag 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 comprises the following steps: S101, completely immerse nano-silicon dioxide in a silane coupling agent solution for 5-60 min, then add surface-roughened glass fiber, and ultrasonically treat for 10-60 min, then filter, wash the filtered product with sufficient deionized water, and dry 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 1-3 h, and vacuum dry at 40-50°C to constant weight to obtain modified glass fiber; The impregnation solution comprises acrylic acid, cellulose ether, polyacrylamide, and deionized water; The mass ratio between cellulose ether, acrylic acid, polyacrylamide, and deionized water is 1:(3-8):(0.5-2):(40-80); The inorganic activator is one of carbide slag powder, saponification waste slag powder, and caustic mud powder; and the mud activator is waste stone powder.

2. The high-fluidity mud / fine tailings slurry backfill early strength solidifying agent according to claim 1, characterized in that, The concentration of the silane coupling agent solution in step S101 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 tailings slurry backfill early strength solidifying agent according to claim 2, characterized in that, The mass ratio between nano-silicon dioxide, surface-roughened glass fiber, and ethylene glycol in step S101 is 1:(2-4):(20-30).

4. The high fluidity mud / fine tailings backfill early strength solidifying agent according to claim 1, characterized in that, The specific treatment steps of the surface-roughened glass fiber in step S101 are as follows: completely immerse the glass fiber in a 1 wt% ethanol solution of tetramethylammonium hydroxide for 1.5 h.

5. The high-fluidity mud / fine tailings slurry backfill early strength solidifying agent according to claim 4, characterized in that, The glass fiber is simultaneously subjected to microwave treatment during the immersion treatment in the ethanol solution of tetramethylammonium hydroxide, and the power of the microwave is 600 W.

6. The high fluidity mud / fine tailings backfill early strength solidifying agent according to claim 1, characterized in that, The cellulose ether in step S102 is specifically selected to be hydroxypropyl methyl cellulose.

7. The high fluidity mud / fine tailings backfill early strength solidifying agent according to claim 1, characterized in that, The accelerator is one of sodium silicate, calcium formate, lithium carbonate, and sodium carbonate; and 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.

8. A process for the preparation of high flow state mud / fine tailings backfilling early strength solidifying agent as claimed in any one of claims 1 to 7, wherein, The method comprises the following steps: S1, weigh cement, inorganic activator, mud activator, accelerator, and water reducing agent according to the proportions, and stir them in a stirrer for 5-15 min to prepare a premix; S2, add water-granulated slag powder, silicon-calcium slag powder, industrial byproduct waste gypsum, gasification slag powder, and modified glass fiber to the premix prepared in step S1 according to the mass fraction, and continue to stir for 10-30 min to prepare a backfilling early strength curing agent.

9. Application of the high-flowability mud / fine mud tailings backfilling early strength curing agent according to any one of claims 1-7 in curing high-flowability mud and fine mud tailings.

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