Copper mine tailing curing agent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of road building materials, and discloses a copper mine tailing curing agent and a preparation method and application thereof. The copper mine tailing curing agent comprises the following components in percentage by weight: 25-40% of sulfonated oil, 30-45% of an emulsifier, 14-22% of a water repellent agent, 0.1-0.5% of hydrolytic polymaleic anhydride, 8-10% of polyethylene glycol and the balance of a sodium lignin sulfonate aqueous solution with the concentration of 8%. According to the curing agent provided by the invention, the compact compression resistance and the water-resistant stability of the copper mine tailings can be remarkably improved, the aim of comprehensively meeting the engineering technical standard is achieved, and the concepts of material saving, energy saving and environmental protection are achieved. The device has the advantages of material and energy conservation, convenience in use, economy, environment friendliness and the like. The curing agent can be widely applied to treatment of tailing resources of various mine tailing ponds, the tailings are turned into wealth, and the effect that multiple purposes are achieved at one stroke is achieved.

Description

Technical Field

[0001] The embodiments of the present invention relate to the technical field of road construction materials, and in particular to a copper tailings curing agent and a preparation method and application thereof. Background Art

[0002] Copper tailings are sandy granular waste produced after ore dressing and grinding. Its treatment is one of the problems that mineral manufacturers need to solve urgently. The common treatment method is to dump it directly in low-lying areas, but the dumping sites are limited, and the heavy metals remaining in copper tailings will seriously threaten groundwater safety.

[0003] At a time when mineral resources are becoming increasingly scarce and environmental problems are becoming increasingly severe, the comprehensive development and management of secondary resources, especially the recovery and utilization of tailings resources, can not only reduce the area occupied by tailings stacking, save costs such as flood control and dam construction, but also improve the environment and safety of mining areas, while achieving "waste to treasure" and creating considerable economic benefits. Therefore, improving the engineering performance of copper mine tailings and turning them into treasure has become an urgent need. Summary of the invention

[0004] To this end, an embodiment of the present invention provides a copper tailings solidifying agent and a preparation method and application thereof.

[0005] In order to achieve the above purpose, the embodiment of the present invention provides the following technical solutions:

[0006] According to a first aspect of an embodiment of the present invention, the present invention provides a copper tailings solidifying agent, wherein the copper tailings solidifying agent comprises, by weight percentage:

[0007] Sulfonated oil 25-40%, emulsifier 30-45%, water repellent 14-22%, hydrolyzed polymaleic anhydride 0.1-0.5%, polyethylene glycol 8-10%, and the balance is 8% sodium lignin sulfonate aqueous solution.

[0008] Furthermore, the emulsifier is polyoxyethylene fatty acid ester, preferably polyoxyethylene oleate.

[0009] Furthermore, the water repellent is selected from one or more of propylene glycol block polyether, siloxane, and methyl silicate.

[0010] Furthermore, the propylene glycol block polyether includes propylene glycol block polyether L44 or L62, the siloxane is polydimethylsiloxane, and the methyl silicate includes sodium methyl silicate or potassium methyl silicate.

[0011] Furthermore, the water repellent is composed of propylene glycol block polyether and siloxane or methyl silicate in a mass ratio of 0.6-1.75.

[0012] According to a second aspect of an embodiment of the present invention, the present invention provides a method for preparing a copper tailings solidifying agent as described in any one of the above items, the method comprising:

[0013] Mixing the sulfonated oil and the emulsifier to obtain a first mixture;

[0014] Mixing the water repellent, hydrolyzed polymaleic anhydride and polyethylene glycol to obtain a second mixture;

[0015] The first group of mixtures, the second group of mixtures and the sodium lignin sulfonate aqueous solution are mixed to obtain the copper mine tailings solidifying agent.

[0016] According to a third aspect of an embodiment of the present invention, the present invention provides use of the copper tailings curing agent as described in any one of the above items in a roadbed water-stabilizing layer material.

[0017] Furthermore, the roadbed water-stabilizing layer material is used for base construction, hardening of soft soil sites, dam consolidation and slope protection of water conservancy projects, fluid filling of fertilizer troughs and pipe galleries, and pressing of unfired bricks.

[0018] According to the fourth aspect of an embodiment of the present invention, the present invention provides a roadbed water-stabilizing layer material based on any of the copper tailings curing agents described above, comprising the following components in parts by weight: 100 parts of copper tailings, 4-6 parts of cement, and 0.01-0.02 parts of copper tailings curing agent.

[0019] Furthermore, it also includes 0.1-3 parts of quicklime powder.

[0020] The present invention uses sulfonated oil as the main raw material, and is matched with emulsifier, water repellent, hydrolyzed polymaleic anhydride, polyethylene glycol, and sodium lignin sulfonate. The dosage of each component is appropriate, and the compatibility design is ingenious and reasonable. A certain degree of saponification reaction is generated during the production process, which effectively suppresses the negative effect of sulfonated oil on weakening the binding force of copper tailings particles, and maintains the amphiphilic properties of sulfonated oil. Its hydrophilic head is adsorbed on the strongly bound water layer on the surface of the copper tailings particles, and the hydrophobic tail forms a coating layer around the surface of the copper tailings particles, which not only reduces the thickness of the bound water layer of the copper tailings particles, which is beneficial to the polymerization of the copper tailings, but also hinders the entry of water to keep it stable.

[0021] The present invention uses an emulsifier, fatty acid polyoxyethylene ester, and a neutralizer, polyethylene glycol. These two materials play an emulsifying, saponifying, and neutralizing role in the process of preparing a composite curing agent. Among them, the often-ignored surface activity function also plays a significant role here. This surface activity function enables the product to easily penetrate between copper tailings particles when it is added to the copper tailings to be solidified, overcome the electric potential and repulsion between the copper tailings particles, reduce the thickness of the copper tailings combined water layer, reduce the capillary force of the copper tailings and the tension on the particle surface, and make the copper tailings more polymerized, more resistant to extrusion, and dense.

[0022] Organic and inorganic materials act together on the copper tailings binder, solving the defect of low compressive strength of copper tailings solidified by simple ions. Organic active agents reduce the thickness of the water layer binding the copper tailings particles, which can guide cement hydrates to penetrate into the copper tailings particles, thereby improving the bonding strength and firmness.

[0023] The present invention is well integrated with water-resistant materials such as methyl silicate / siloxane. These two materials can react with CO in the air. 2 Or other acidic compounds react to form an insoluble mesh waterproof layer inside the copper tailings material, which solves the problem of copper tailings aggregate collapse when encountering water. The solidified copper tailings body is therefore water-resistant and stable, and ensures the stability of freeze-thaw.

[0024] Methyl silicate and siloxane can also function as alkali activators, reacting with minerals in the binder to form volcanic ash, causing micro-expansion and making the solidified copper tailings more compact and resistant to compression. Its micro-pores are filled with gel substances such as sodium lignin sulfonate and cement hydrate, further enhancing the compactness and water resistance.

[0025] The sodium lignin sulfonate used in the present invention not only has a gel body with a bonding effect on the powder particles, but also has an adsorption and dispersion effect on the cement used in combination, thereby improving the physical properties of the cement and enhancing its effect.

[0026] The embodiments of the present invention have the following advantages:

[0027] 1. Most of the materials used in the present invention are rich in organic active ingredients, which play a key role in changing the surface ionic state of copper tailings, improving the binding force of copper tailings, and enabling copper tailings to obtain better engineering properties.

[0028] 2. The second group of mixtures provides alkaline conditions for the moderate saponification reaction of the first group of mixtures. A certain degree of saponification reaction can reduce the side effects of oil and ester components in the material, so that it maintains hydrophobic properties while not destroying the bonding strength of copper tailings particles. This alkalinity can also stimulate the minerals in the copper tailings and inorganic binders, causing micro-expansion, making the copper tailings solidified body more compact and resistant to compression.

[0029] 3. Propylene glycol block polyether L44 or L62 and siloxane or sodium (potassium) methyl silicate are all excellent water-resistant materials. The combination of the two, plus the hydrophobicity of other "amphiphilic" materials (sulfonated oil and emulsifier), enriches the water-resistant methods and improves the water-resistant, antifreeze and stability effects.

[0030] 4. Polyethylene glycol and hydrolyzed polymaleic anhydride play a role in adjusting pH and neutralizing. The degree of saponification reaction can be controlled by mastering the dosage ratio.

[0031] 5. This curing agent is used in combination with an inorganic binder. P.O425 ordinary Portland cement is preferred as the inorganic binder, and the commonly used amount is 4-6% of the mass of the copper tailings. The inorganic binder participates in the cementation reaction in the solidified mixture to form hydrated gel and other hydrated silicate substances, further enhancing the strength of the soil structure. A small amount of quicklime (0.1-3% of the mass of the copper tailings) can also be added to depolymerize the copper tailings to facilitate the diffusion of the curing agent in the copper tailings.

[0032] The curing agent provided by the present invention can significantly improve the compaction and compression resistance and water resistance of copper mine tailings, aiming to fully meet engineering technical standards and upholding the concepts of material saving, energy saving and environmental protection. It has the advantages of material saving and energy saving, convenient use, economic and environmental protection. The curing agent can be widely used in processing tailings resources of various mine tailings ponds, turning tailings into treasures, and achieving multiple benefits at one stroke. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the implementation methods of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the implementation methods or the description of the prior art. Obviously, the drawings in the following description are only exemplary, and for ordinary technicians in this field, other implementation drawings can be derived from the provided drawings without creative work.

[0034] Figure 1 The invention provides the copper tailings solidified soil coring. DETAILED DESCRIPTION

[0035] The following is a description of the implementation of the present invention by specific embodiments. People familiar with the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] Example 1

[0037] This embodiment provides a copper tailings solidifying agent, which includes the following raw materials by weight percentage:

[0038] Sulfonated oil 35%, polyoxyethylene oleate 30%, propylene glycol block polyether L44 14%, polydimethylsiloxane 8%, hydrolyzed polymaleic anhydride 0.3%, polyethylene glycol 8%, and the balance is 8% sodium lignin sulfonate aqueous solution.

[0039] The preparation method of the above copper ore tailings solidifying agent is as follows:

[0040] (1) mixing sulfonated oil and polyoxyethylene oleate to obtain a first mixture;

[0041] (2) mixing propylene glycol block polyether L44, polydimethylsiloxane, hydrolyzed polymaleic anhydride and polyethylene glycol to obtain a second mixture;

[0042] (3) The first group of mixtures in step (1), the second group of mixtures in step (2) and the sodium lignin sulfonate aqueous solution are mixed to obtain a copper mine tailings solidifying agent.

[0043] Example 2

[0044] This embodiment provides a copper tailings solidifying agent, which includes the following raw materials by weight percentage:

[0045] Sulfonated oil 40%, polyoxyethylene oleate 30%, propylene glycol block polyether L44 6%, sodium methyl silicate 8%, hydrolyzed polymaleic anhydride 0.2%, polyethylene glycol 8%, and the balance is 8% sodium lignin sulfonate aqueous solution.

[0046] The preparation method of the copper ore tailings solidifying agent is the same as that of Example 1.

[0047] Example 3

[0048] This embodiment provides a copper tailings solidifying agent, which includes the following raw materials by weight percentage:

[0049] Sulfonated oil 25%, polyoxyethylene oleate 45%, propylene glycol block polyether L62 10%, sodium methyl silicate 6%, hydrolyzed polymaleic anhydride 0.2%, polyethylene glycol 8%, and the balance is 8% sodium lignin sulfonate aqueous solution.

[0050] The preparation method of the copper ore tailings solidifying agent is the same as that of Example 1.

[0051] Example 4

[0052] This embodiment provides a copper tailings solidifying agent, which includes the following raw materials by weight percentage:

[0053] Sulfonated oil 35%, polyoxyethylene oleate 35%, propylene glycol block polyether L62 8%, potassium methyl silicate 6%, hydrolyzed polymaleic anhydride 0.2%, polyethylene glycol 10%, and the balance is 8% sodium lignin sulfonate aqueous solution.

[0054] The preparation method of the copper ore tailings solidifying agent is the same as that of Example 1.

[0055] Example 5

[0056] This embodiment provides a copper tailings solidifying agent, which includes the following raw materials by weight percentage:

[0057] Sulfonated oil 30%, polyoxyethylene oleate 35%, propylene glycol block polyether L44 8%, polydimethylsiloxane 12%, hydrolyzed polymaleic anhydride 0.3%, polyethylene glycol 8%, and the balance is 8% sodium lignin sulfonate aqueous solution.

[0058] The preparation method of the copper ore tailings solidifying agent is the same as that of Example 1.

[0059] Comparative Example 1

[0060] This comparative example provides a copper tailings curing agent. Compared with Example 1, Comparative Example 1 mainly replaces polydimethylsiloxane with potassium metasilicate and replaces hydrolyzed maleic anhydride with aluminum dihydrogen phosphate.

[0061] Specifically, by weight percentage, Comparative Example 1 includes the following raw materials:

[0062] Sulfonated oil 34%, potassium metasilicate 12%, polyoxyethylene oleate 26%, propylene glycol block polyether L44 8%, polyethylene glycol 14%, aluminum dihydrogen phosphate 2%, and the balance is 8% sodium lignin sulfonate aqueous solution.

[0063] The preparation method of the above copper ore tailings solidifying agent is as follows:

[0064] (1) First, sulfonated oil and potassium metasilicate are mixed evenly, and then oleic acid polyoxyethylene is added and mixed evenly to obtain a first group of mixtures;

[0065] (2) Propylene glycol block polyether L44 and polyethylene glycol are mixed evenly, and then aluminum dihydrogen phosphate is added and mixed evenly to obtain a second group of mixtures;

[0066] (3) The first group of mixtures in step (1), the second group of mixtures in step (2) and the sodium lignin sulfonate aqueous solution are mixed to obtain a copper mine tailings solidifying agent.

[0067] Comparative Example 2

[0068] This comparative example provides a copper tailings curing agent. Compared with Example 1, Comparative Example 2 mainly uses sodium petroleum sulfonate to replace sulfonated oil. Specifically, by weight percentage, Comparative Example 2 includes the following raw materials:

[0069] 36% sodium petroleum sulfonate, 12% polydimethylsiloxane, 26% polyoxyethylene oleate, 48% propylene glycol block polyether L4, 15% polyethylene glycol, 0.3% hydrolyzed maleic anhydride, and the balance is 8% sodium lignin sulfonate aqueous solution.

[0070] The preparation method of the above copper ore tailings solidifying agent is as follows:

[0071] (1) First, sulfonated oil and polydimethylsiloxane are mixed evenly, and then oleic acid polyoxyethylene is added and mixed evenly to obtain a first group of mixtures;

[0072] (2) Propylene glycol block polyether L44 and polyethylene glycol are mixed evenly, and then hydrolyzed maleic anhydride is added and mixed evenly to obtain a second group of mixtures;

[0073] (3) The first group of mixtures in step (1), the second group of mixtures in step (2) and the sodium lignin sulfonate aqueous solution are mixed to obtain a copper mine tailings solidifying agent.

[0074] Test Example 1

[0075] Solidified soil test program

[0076] This test aims to determine the material mix ratio through experiments for different soil materials and different application scenarios, and to prepare them according to the established plan. The specific basic mix ratio and experimental steps are as follows:

[0077] 1. Prepare the ingredients

[0078] 1000 portions of copper mine tailings were prepared. The optimum moisture content and maximum dry density of the soil were obtained through compaction test. When preparing the materials, the moisture content of the soil needs to be reduced to below the optimum moisture content so that the remaining water can be used to dilute the curing agent.

[0079] Curing agent: prepare 0.2 parts of each of the curing agent of Examples 1-5 and Comparative Examples 1-2.

[0080] Water: Prepare > 60 parts of clean water to dilute the curing agent.

[0081] Cement: Prepare 60 parts of P.O42.5 cement.

[0082] Powdered quicklime: Prepare 30 portions.

[0083] 2. Preparation

[0084] Step 1: If the soil is sticky and lumpy, add lime to the soil and stir evenly.

[0085] Step 2: Calculate the amount of water to be added based on the actual moisture content and optimal moisture content of the soil. Dilute the curing agent in water, stir evenly, spray it on the soil with a spray pot, stir evenly again, and then keep it in a sealed container for 24-48 hours.

[0086] Step 3: Add the prepared cement, mix well and set aside.

[0087] 3. Suppression

[0088] Load the prepared material into a mold (50mm×50mm cylindrical, 216g of mixed material is required for one specimen), compact it using a machine to ensure that the compaction degree is ≥95%, and then demold it to finalize the shape.

[0089] 4. Maintenance

[0090] Place the formed specimens in a constant temperature and humidity curing box (temperature 20±2℃, humidity ≥95%) for curing. After 6 days of curing, take out one-third of the specimens for testing, and immerse the remaining two-thirds of the specimens in water and take them out of the water after immersion for 24 hours.

[0091] 5. Detection

[0092] One third of the specimens taken out before entering the water were weighed and tested for compressive strength, and the data were recorded in detail.

[0093] The specimens soaked in water were weighed and tested for compressive strength. In addition, the remaining specimens that were not tested were cured for 28 days and tested for compressive strength again. Finally, the compressive strength and water stability were calculated.

[0094] The test and calculation are based on the "Testing Procedures for Stabilized Materials of Inorganic Binders for Highway Engineering" (JTG 3441-2024). Water absorption = mass of the specimen after 24 hours of immersion - mass of the specimen before immersion; water stability = compressive strength value of the specimen after 24 hours of immersion / compressive strength value of the specimen before immersion. The higher the water stability coefficient, the stronger the water resistance and water resistance.

[0095] The water absorption test results are shown in Table 1 below, wherein the blank control is the one without adding the copper tailings solidifying agent.

[0096] Table 1

[0097]

[0098] The results show that the test piece provided by the embodiment of the present invention has low water absorption and water stability ≥80%, which meets the national standard.

[0099] The results of the 7-day and 28-day unconfined compressive strength tests are shown in Table 2 below, where the blank control is the one without the addition of the copper tailings solidifying agent.

[0100] Table 2

[0101]

[0102] The results show that the unconfined compressive strength of the specimen provided by the embodiment of the present invention is ≥2.96MPa at 7 days and ≥4.83MPa at 28 days, which fully meets the medium and light traffic load requirements for expressways and first-class highway bases, as well as the heavy traffic load requirements for second-class and below highway bases.

[0103] Test Example 2

[0104] Leaching test

[0105] The solidified copper tailings mixture obtained by using the solidifying agent in Example 1 was subjected to a leaching test, and the results are shown in Table 3 below.

[0106] Table 3

[0107]

[0108] After testing, the leachate index fully complies with the national standard (DB34 / T 4994-2025). The test results of Examples 2-5 are not significantly different from those of Example 1. The above content shows that the solidified copper tailings mixture provided by the present invention is highly safe as an engineering material, non-toxic, harmless, and will not cause any pollution to the environment.

[0109] Copper tailings, also known as copper mine tailings, are powdery or gravel-like solid waste produced after natural copper ore is crushed, sorted, and selected. Copper tailings contain quartz, calcite, chalcopyrite, dolomite and other components, among which Si, Al, Fe and other elements account for a large proportion, which is similar to traditional road construction materials in composition, providing a good foundation for its application in road engineering. The copper tailings used this time come from the Chuzhou Tongxin Mining Tailings Reservoir. The copper tailings are fine in particle size, gray-yellow powder, with a natural moisture content of 1.9%, and the composition is mainly SiO 2 , Fe 2 O 3 , CaO, Al 2 O 3 These compounds are mainly Fe 2 O 3 , CaO, Al 2 O 3 Etc. have certain activity, and can form a material with certain strength, rigidity and durability after reacting with a curing agent and a binder. In addition, these components are similar to the components of natural sand and gravel aggregates, so it is reasonable to use the copper tailings in road engineering after improvement. From the perspective of physical and mechanical properties, the copper tailings have a small particle size and a large weight. In order to improve its cohesion, the curing agent provided by the present invention can improve the compaction characteristics and structural stability of the mixture, so that the copper tailings improved soil can meet the requirements of relevant specifications. It is stipulated in the "Technical Specifications for Construction of Highway Pavement Base" (JTG-T-F20-2015) that the base material should meet the requirements of small compression rate, certain strength, rigidity, durability, and good water stability. From the perspective of environmental impact, the curing agent provided by the present invention can capture most of the free metal particles to form a stable complex, and effectively seal it in the solidified soil body, thereby greatly reducing the toxicity of harmful components such as heavy metals to the environment. This result has been verified by experiments and engineering.

[0110] The technical solution provided by the present invention was put into practical application in the S331 K21 + 970 - K22 + 70 section of Xianghe Town, Quanjiao County. Figure 1(complete, no debris, qualified compaction, high density, good integrity), the product has undergone strict environmental protection and engineering tests, and the indicators are fully up to standard.

[0111] Although the present invention has been described in detail above by general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A copper ore tailings solidifying agent, characterized in that: The copper ore tailings solidifying agent comprises, by weight percentage: Sulfonated oil 25-40%, emulsifier 30-45%, water repellent 14-22%, hydrolyzed polymaleic anhydride 0.1-0.5%, polyethylene glycol 8-10%, and the balance is 8% sodium lignin sulfonate aqueous solution.

2. The copper ore tailings curing agent according to claim 1, characterized in that The emulsifier is polyoxyethylene fatty acid ester.

3. The copper ore tailings curing agent according to claim 1, characterized in that The water repellent is selected from one or more of propylene glycol block polyether, siloxane, and methyl silicate.

4. The copper ore tailings curing agent according to claim 3, characterized in that: The propylene glycol block polyether includes propylene glycol block polyether L44 or L62, the siloxane is polydimethylsiloxane, and the methyl silicate includes sodium methyl silicate or potassium methyl silicate.

5. The copper ore tailings curing agent according to claim 3, characterized in that: The water repellent is composed of propylene glycol block polyether and siloxane or methyl silicate in a mass ratio of 0.6-1.

75.

6. The method for preparing the copper tailings curing agent according to any one of claims 1 to 5, characterized in that: The method comprises: Mixing the sulfonated oil and the emulsifier to obtain a first mixture; Mixing the water repellent, hydrolyzed polymaleic anhydride and polyethylene glycol to obtain a second mixture; The first group of mixtures, the second group of mixtures and the sodium lignin sulfonate aqueous solution are mixed to obtain the copper mine tailings solidifying agent.

7. Use of the copper tailings curing agent according to any one of claims 1 to 5 in roadbed water-stabilizing layer materials.

8. The use according to claim 7, characterized in that: The roadbed water-stabilizing layer material is used for base construction, hardening of soft soil sites, dam consolidation and slope protection of water conservancy projects, fluid filling of fertilizer troughs and pipe galleries, and pressing of unburned bricks.

9. A roadbed water-stabilizing layer material based on the copper mine tailings curing agent according to any one of claims 1 to 5, characterized in that: The invention comprises the following components in parts by weight: 100 parts of copper ore tailings, 4-6 parts of cement and 0.01-0.02 parts of copper ore tailings curing agent.

10. The roadbed water-stabilizing layer material according to claim 9, characterized in that: It also includes 0.1-3 parts of quicklime powder.

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