Preparation method of composite anti-seepage material and its products and applications

Abstract

This disclosure relates to the field of seepage-proof materials technology, providing a method for preparing a composite seepage-proof material, its product, and its application. The method for preparing the composite seepage-proof material includes: mixing a first component with an acidic sodium silicate solution to obtain a mixed solution; and mixing a second component with the mixed solution to obtain the composite seepage-proof material; wherein the first component includes a first main agent, a crosslinking agent, a retarder, and an accelerator; the first main agent includes an aqueous solution of a first acrylate, the first acrylate including at least one of calcium acrylate and magnesium acrylate; the second component includes an initiator; the initiator including at least one of ammonium persulfate and sodium persulfate. The composite seepage-proof material provided by this disclosure, by compounding acrylate with acidic sodium silicate, achieves at least the following effects: simple preparation method, high compressive strength, high later-stage stability, good seepage-proof effect, good durability, uniform liquid, environmental friendliness, and low cost, and can be applied to seepage prevention in ion-adsorption rare earth mines.

Description

Technical Field

[0001] The present disclosure relates to the technical field of anti-seepage materials, and in particular to a preparation method of a composite anti-seepage material and a product and application thereof. Background Art

[0002] Anti-seepage materials are the main raw materials for grouting construction. At present, conventional anti-seepage materials include cement, clay, water glass and organic chemical grouting materials. Among them, cement and clay anti-seepage materials are difficult to meet the different requirements of different strata due to their large particle size and low groutability; epoxy resin, phenolic resin and polyurethane chemical anti-seepage materials are not only costly, but also have a certain degree of toxicity, which can easily pollute the environment and endanger human health; acrylate chemical anti-seepage materials are a new hydrophilic gel in recent years, which have the advantages of environmental friendliness, low initial viscosity and high groutability, so they have good application prospects, but they still have the disadvantage of high cost; water glass anti-seepage materials have a long history as grouting materials due to their non-toxicity, low cost and convenient construction. However, for special anti-seepage construction projects such as ionic rare earth mines, the shallow grouting of the water-rich / permeable sandy soil layer is prone to slurry leakage and difficulty in pressurization, making it extremely difficult to prevent seepage. Therefore, conventional anti-seepage materials are difficult to meet the on-site grouting construction needs of ionic rare earth mines.

[0003] Chinese patent document CN201910223478.3, application date 20190322, entitled "A water glass-acrylate composite gel water plugging agent and its preparation method", discloses a composite gel water plugging agent, including liquid A and liquid B; wherein liquid A is an acrylate monomer main agent, water glass, a cross-linking agent and a promoter; liquid B is an initiator and an auxiliary agent; the acrylate monomer main agent is selected from any one or more of sodium acrylate, calcium acrylate, and magnesium acrylate; the promoter is selected from any one of triethanolamine, tetramethylethylenediamine, calcium formate, calcium chloride, and calcium nitrite; the auxiliary agent is selected from one or more of copper sulfate, alum, and calcium chloride.

[0004] The above patent document forms a composite gel water plugging agent with multiple properties by compounding acrylate and water glass. However, the composite gel water plugging agent has disadvantages such as poor durability and complicated preparation process. In addition, due to its strong alkalinity, the formed anti-seepage body has a certain amount of alkali dissolution, which is also easy to cause alkali pollution. It can be seen that the above composite gel water plugging agent is not suitable for anti-seepage of ionic rare earth mines, especially anti-seepage of water-rich / permeable sandy soil layers in ionic rare earth mines.

[0005] In summary, there is an urgent need for an anti-seepage material that can at least achieve the characteristics of simple preparation method, high compressive strength, high later stability, good anti-seepage effect, good durability, uniform liquid, environmental friendliness and low cost, and can be applied to the anti-seepage effect of ionic rare earth mines. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the anti-seepage materials in the prior art, such as poor durability, complicated preparation process, easy pollution, high cost and unsuitability for anti-seepage in ionic rare earth mines, and to provide a preparation method of a composite anti-seepage material and its products and applications, so as to at least achieve the effects of simple preparation method, high compressive strength, high later stability, good anti-seepage effect, good durability, uniform liquid, environmental friendliness and low cost, and can be applied to the anti-seepage effect of ionic rare earth mines.

[0007] The purpose of this disclosure is achieved through the following technical solutions:

[0008] On the one hand, a preparation method of a composite anti-seepage material is provided. The preparation method comprises: mixing a first component with an acidic sodium silicate solution to obtain a mixed solution; and mixing a second component with the mixed solution to obtain the composite anti-seepage material. The first component comprises a first main agent, a cross-linking agent, a retarder and an accelerator; the first main agent comprises an aqueous solution of a first acrylate, and the first acrylate comprises at least one of calcium acrylate and magnesium acrylate; the second component comprises an initiator; the initiator comprises at least one of ammonium persulfate and sodium persulfate; the volume ratio of the first component, the second component and the acidic sodium silicate solution is 1:0.5-2:0.5-4.

[0009] The preparation method provided by the present disclosure firstly mixes the acidic sodium silicate solution with the first component containing the first acrylate, so as to compound the acidic sodium silicate (i.e., acidic water glass) with the acrylate, and obtain the mixed liquid which is homogeneously distributed in the form of a transparent solution and free of particles or sol particles; on this basis, the mixed liquid is then mixed with the second component containing the initiator, and the initiator can react with the cross-linking agent and the accelerator to promote the polymerization reaction of the acrylic acid monomer to form a gel, thereby obtaining the composite anti-seepage material, and finally achieving the effects of simple preparation method, high compressive strength, high later stability, good anti-seepage effect, good durability, uniform liquid, environmental friendliness and low cost.

[0010] It should be understood that the acidic sodium silicate and the acrylate are both environmentally friendly anti-seepage materials. Therefore, compounding the two can make the finally prepared composite anti-seepage material have the advantage of being environmentally friendly; at the same time, the addition of the acidic sodium silicate can also reduce the amount of the acrylate to a certain extent, thereby reducing the preparation cost of the composite anti-seepage material; in addition, the acrylate and the acidic sodium silicate both have the advantage of low initial viscosity. Therefore, the composite anti-seepage material with the acrylate and the acidic sodium silicate as main components also has the advantage of low initial viscosity.

[0011] It should be noted that the mixed liquid is homogeneously distributed in the form of a transparent solution and does not contain particles or sol particles, which makes the initial viscosity of the composite anti-seepage material lower and the permeability stronger. Therefore, the diffusion radius of the composite anti-seepage material in the grouting process (for example, the grouting process of the water-rich / permeable sand layer of an ionic rare earth mine) is larger, which can increase the design value of the grouting hole spacing, thereby achieving the effect of reducing construction costs.

[0012] It is worth noting that, with respect to the preparation method provided in the present disclosure, the inventors of the present disclosure have discovered at least the following working principles after research:

[0013] 1. Synergistic effect of the acidic sodium silicate and the acrylate: On the one hand, the silicon-oxygen structure provided by the acidic sodium silicate can maintain a good molding effect, thereby effectively reducing the volume phase change of the acrylate; on the other hand, the acrylate can also improve the water retention capacity and weathering resistance of the acidic sodium silicate; on this basis, by limiting the volume ratio of the first component, the second component and the acidic sodium silicate, it is possible to avoid a decrease in the compressive strength and weathering resistance of the composite anti-seepage material due to excessive addition of the acidic sodium silicate while ensuring that the volume phase change of the acrylate is effectively reduced, and at the same time, it is possible to effectively reduce the cost.

[0014] 2. Synergistic effect of the acidic sodium silicate and the retarder: by adding the retarder to the first component, the gelling time of the acrylate can be regulated (for example, slowed down), and on this basis, by adding the acidic sodium silicate when preparing the mixed solution, the gelling time of the acrylate can be further regulated (for example, slowed down); that is, the retarder and the acidic sodium silicate can synergistically enhance their effectiveness to better regulate (for example, slow down) the gelling time of the acrylate, thereby better regulating (for example, slowing down) the gelling time of the composite anti-seepage material.

[0015] 3. Other functions of the acidic sodium silicate: The addition of the acidic sodium silicate can also improve the tolerance of the composite anti-seepage material to acidic liquids, thereby ensuring the long-term stability of the anti-seepage effect of the composite anti-seepage material in the later stage.

[0016] It should be noted that water glass anti-seepage materials generally include alkaline water glass gelled in alkaline areas, neutral water glass gelled in neutral areas, and acidic water glass gelled in acidic areas. However, alkaline water glass gelled in alkaline areas has strong alkali dissolution, so there is a certain amount of alkali pollution, and its durability is poor; neutral water glass gelled in neutral areas has the fastest gelling speed and extremely poor permeability, so only a two-liquid grouting method can be adopted; acidic water glass gelled in acidic areas has advantages such as environmental friendliness and controllable gelling time, but it still has disadvantages such as low compressive strength and easy weathering and disintegration. In this regard, the preparation method provided by the present disclosure can overcome the shortcomings of acidic water glass while maintaining the advantages of acidic water glass itself by formulating the components of the composite anti-seepage material.

[0017] In some examples, the initiator includes one of the ammonium persulfate and the sodium persulfate.

[0018] It is easy to understand that the present disclosure does not limit the method for preparing the first component, and any method that can prepare the first component is included in the protection scope of the present disclosure.

[0019] In some examples, the method for preparing the first component includes: adding the cross-linking agent, the retarder and the accelerator to the first main agent and mixing them evenly.

[0020] In some embodiments, the pH of the acidic sodium silicate solution is 2-4.

[0021] Exemplarily, the pH of the acidic sodium silicate solution is 2.0, 2.2, 2.5, 2.7, 3.0, 3.3, 3.5, 3.8 or 4.0.

[0022] In the above embodiment, by limiting the pH of the acidic sodium silicate, not only the gelling time of the acidic sodium silicate can be further regulated (for example, slowed down), but also the gelling time of the acrylate can be further regulated (for example, slowed down), thereby further regulated (for example, slowed down) the gelling time of the composite anti-seepage material.

[0023] In some embodiments, the method for preparing the acidic sodium silicate solution comprises: mixing sodium silicate with water to obtain a sodium silicate solution; and mixing a sulfuric acid solution with the sodium silicate solution to obtain the acidic sodium silicate solution. The modulus of the sodium silicate is 2.6 to 3.3; the Baume degree of the sodium silicate solution is 10 to 25 Be°; and the mass fraction of sulfuric acid in the sulfuric acid solution is 5% to 15%.

[0024] Exemplarily, the modulus of the sodium silicate is 2.6, 2.8, 3.0 or 3.3.

[0025] Exemplarily, the Baume degree of the sodium silicate solution is 10Be°, 15Be°, 20Be° or 25Be°.

[0026] Exemplarily, the mass fraction of sulfuric acid in the sulfuric acid solution is 5%, 8%, 10%, 12% or 15%.

[0027] In the above embodiment, by limiting the modulus of the sodium silicate, the Baume degree of the sodium silicate solution and the mass fraction of sulfuric acid in the sulfuric acid solution, the cost can be controlled while ensuring the performance of the composite anti-seepage material in terms of strength and gel time.

[0028] In some embodiments, the mass fraction of the first acrylate in the first main agent is 10% to 40%.

[0029] Exemplarily, the mass fraction of the first acrylate in the first main agent is 10%, 15%, 20%, 25%, 30%, 35% or 40%.

[0030] In the above embodiment, by limiting the mass fraction of the first acrylate, the cost can be controlled while ensuring the performance of the composite anti-seepage material in terms of strength and other aspects.

[0031] In some embodiments, the second component further includes a second main agent; the second main agent includes an aqueous solution of a second acrylate, and the second acrylate is the same as the first acrylate.

[0032] In the above embodiment, by adding the second main agent into the second component, the initiator can be dispersed by the second main agent; meanwhile, the second acrylate is the same as the first acrylate, so it is more convenient for practical operation.

[0033] It should be noted that, when the second component also includes the second main agent, the volume ratio of the first component to the second component is still 1:0.5-2.

[0034] In some examples, the volume ratio of the first component to the second component may be 1:0.5, 1:1, or 1:2.

[0035] For example, the volume ratio of the first component to the second component may be 1: 1. In this case, the volumes of the first component and the second component are closer, thereby achieving the effect of making the operation process of the preparation method simpler, the distribution of each component more uniform, and the gel reaction more uniform.

[0036] In some embodiments, the mass fraction of the second acrylate in the second main agent is equal to the mass fraction of the first acrylate in the first main agent.

[0037] It should be noted that, since the second acrylate is the same as the first acrylate, "the mass fraction of the second acrylate in the second main agent is equal to the mass fraction of the first acrylate in the first main agent" means that the mass fraction of any component in the second acrylate in the second main agent is equal to the mass fraction of the corresponding component in the first acrylate in the first main agent.

[0038] In some examples, the first acrylate and the second acrylate both include calcium acrylate and magnesium acrylate, the mass fraction of calcium acrylate in the first main agent is equal to the mass fraction of calcium acrylate in the second main agent, and the mass fraction of magnesium acrylate in the first main agent is equal to the mass fraction of magnesium acrylate in the second main agent.

[0039] It should be noted that, when the first acrylate includes calcium acrylate and magnesium acrylate, the present disclosure does not limit the mass ratio of calcium acrylate to magnesium acrylate. Exemplarily, the mass ratio of calcium acrylate to magnesium acrylate is 3:7.

[0040] In some embodiments, the mass of the initiator is 0.1% to 5% of the mass of the second main agent.

[0041] Exemplarily, the mass of the initiator is 0.1%, 0.5%, 0.8%, 1.0%, 2.0%, 3.0%, 4.0% or 5.0% of the mass of the second main agent.

[0042] In the above embodiment, by limiting the ratio between the mass of the initiator and the mass of the second main agent, not only the gelling time and the gelling effect can be guaranteed, but also the performance of the composite anti-seepage material can be guaranteed.

[0043] It is easy to understand that the present disclosure does not limit the method for preparing the second component, and any method that can prepare the second component is included in the protection scope of the present disclosure.

[0044] In some examples, when the second component includes the initiator and the second main agent, the method for preparing the second component includes: adding the initiator to the second main agent and mixing them evenly.

[0045] In some embodiments, the crosslinking agent includes at least one of N,N′-methylenebisacrylamide, ethylene glycol diacrylate, pentaerythritol diacrylate, divinylbenzene, and diisocyanate.

[0046] In some embodiments, the retarder comprises potassium ferrocyanide.

[0047] In some embodiments, the accelerator includes at least one of triethanolamine and sodium bisulfite.

[0048] In some examples, the accelerator includes one of triethanolamine and sodium bisulfite.

[0049] In some embodiments, the mass of the cross-linking agent is 0.5% to 5% of the mass of the first main agent.

[0050] Exemplarily, the mass of the cross-linking agent is 0.5%, 0.8%, 1.0%, 2.0%, 3.0%, 4.0% or 5.0% of the mass of the first main agent.

[0051] In the above embodiment, by limiting the ratio between the mass of the cross-linking agent and the mass of the first main agent, the cost can be controlled while ensuring the strength of the composite anti-seepage material.

[0052] In some embodiments, the mass of the retarder is 0.1% to 2% of the mass of the first main agent.

[0053] Exemplarily, the mass of the retarder is 0.1%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8% or 2.0% of the mass of the first main agent.

[0054] In the above embodiment, by limiting the ratio between the mass of the retarder and the mass of the first main agent, the gelling time, gelling effect and strength of the composite anti-seepage material can be ensured.

[0055] In some embodiments, the mass of the accelerator is 0.1% to 5% of the mass of the first main agent.

[0056] Exemplarily, the mass of the accelerator is 0.1%, 0.5%, 0.8%, 1.0%, 2.0%, 3.0%, 4.0% or 5.0% of the mass of the first main agent.

[0057] In the above embodiment, the performance of the composite anti-seepage material can be guaranteed by limiting the ratio between the mass of the accelerator and the mass of the first main agent.

[0058] In another aspect, a composite anti-seepage material is provided, wherein the composite anti-seepage material is prepared by the preparation method described in any one of the above embodiments.

[0059] The beneficial effects of the composite anti-seepage material provided in the present disclosure are the same as the beneficial effects of the preparation method provided in the present disclosure, and will not be repeated here.

[0060] On the other hand, there is provided a preparation method described in any one of the above embodiments or an application of the composite anti-seepage material described in any one of the above embodiments in the anti-seepage of ionic rare earth mines.

[0061] In some embodiments, the ionic rare earth mine includes a sand layer. In this case, the anti-seepage can be, for example, the anti-seepage of the sand layer.

[0062] In some examples, the sand layer is a water-rich / permeable sand layer.

[0063] It should be noted that the current grouting methods include single-liquid grouting and double-liquid grouting. Among them, single-liquid grouting is to mix different components in advance and then wait for use, which has the characteristics of long gelation time and large diffusion range; double-liquid grouting is to mix the outlets of different containers containing different components and then directly grout, which has the characteristics of short gelation time (that is, gelation time is uncontrollable) and small diffusion range.

[0064] In view of this, the unique on-site requirements for grouting of the ionic rare earth mine (for example, the sandy soil layer) include limited grouting operating platform, long grouting pipeline, long gelation time and large diffusion range, etc. The above-mentioned on-site requirements determine that the grouting for the purpose of waterproofing the ionic rare earth mine (for example, the sandy soil layer) needs to be achieved by single-liquid grouting.

[0065] In some examples, the single-liquid grouting method includes: mixing the second component with the mixed liquid, and grouting the ionic rare earth mine (e.g., the sand layer), and completing the grouting before gel formation (i.e., before obtaining the composite anti-seepage material).

[0066] The application provided by the present disclosure is to use the composite anti-seepage material for the anti-seepage of the ionic rare earth mine (for example, the sandy soil layer). Since the composite anti-seepage material has the advantages of high compressive strength, high later stability, good anti-seepage effect, good durability, controllable gelling time, environmental friendliness and low cost, the use of the composite anti-seepage material for the anti-seepage can meet the above-mentioned on-site needs, thereby solving the problems of great difficulty and high cost of anti-seepage in the ionic rare earth mine (for example, the sandy soil layer), and can also achieve good anti-seepage effect.

[0067] It should be understood that, in the description of the present disclosure, the acidic sodium silicate refers to the acidic sodium silicate solution.

[0068] In the description of the present disclosure, the acrylate has different meanings in different situations:

[0069] For example, before mixing the mixed liquid with the second component containing the second acrylate, the acrylate refers to the first acrylate; after mixing the mixed liquid with the second component containing the second acrylate, the acrylate refers to the first acrylate and the second acrylate.

[0070] The beneficial effects of the present disclosure are:

[0071] 1. The present invention discloses a method for preparing a composite anti-seepage material. First, the acidic sodium silicate solution is mixed with the first component containing the first acrylate to compound the acidic sodium silicate with the acrylate to obtain the mixed solution which is homogeneously distributed in a transparent solution and free of particles or sol particles. On this basis, the mixed solution is then mixed with the second component containing the initiator to promote the polymerization reaction of the acrylic acid monomer to form a gel by utilizing the reaction of the initiator with the cross-linking agent and the accelerator, thereby obtaining the composite anti-seepage material. The composite anti-seepage material has the advantages of simple preparation method, high compressive strength, high later stability, good anti-seepage effect, good durability, uniform liquid, environmental friendliness and low cost.

[0072] 2. The preparation method of a composite anti-seepage material disclosed in the present invention can maintain a good molding effect by adding the acidic sodium silicate to provide a silicon-oxygen structure, thereby effectively reducing the volume phase change of the acrylate; at the same time, by adding the acrylate, the water retention capacity and weathering resistance of the acidic sodium silicate can also be improved.

[0073] 3. The preparation method of a composite anti-seepage material disclosed in the present invention can better regulate the gelation time of the acrylate through the synergistic effect of the retarder and the acidic sodium silicate, thereby better regulating the gelation time of the composite anti-seepage material.

[0074] 4. The preparation method of a composite anti-seepage material disclosed in the present invention can further regulate the gelation time of the acidic sodium silicate and the gelation time of the acrylate by limiting the pH of the acidic sodium silicate, thereby further regulating the gelation time of the composite anti-seepage material.

[0075] 5. The preparation method of a composite anti-seepage material disclosed in the present invention can improve the tolerance of the composite anti-seepage material to acidic liquid by adding the acidic sodium silicate, thereby ensuring the long-term stability of the anti-seepage effect of the composite anti-seepage material in the later stage. DETAILED DESCRIPTION

[0076] The technical solutions in some embodiments of the present disclosure are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present disclosure, not all of the embodiments. Based on the embodiments provided by the present disclosure, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present disclosure.

[0077] In the following, the terms "first" and "second" are used for descriptive purposes only and are not to be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features.

[0078] When describing some embodiments, the expression "A and / or B" may be used. It is easy to understand that "A and / or B" includes the following three combinations: only A, only B, and a combination of A and B.

[0079] When describing some embodiments, the expressions "at least one of A, B and C" and "at least one of A, B or C" may be used, both of which have the same meaning and include the following combinations of A, B and C: A only, B only, C only, the combination of A and B, the combination of A and C, the combination of B and C, and the combination of A, B and C.

[0080] Example 1

[0081] A method for preparing a composite anti-seepage material, comprising S1 to S4.

[0082] S1. Prepare the first component, including: adding a cross-linking agent, a retarder and an accelerator to the first main agent, and mixing them evenly to obtain; wherein the first main agent is an aqueous solution of a first acrylate, the first acrylate is magnesium acrylate, and the mass fraction of the first acrylate in the first main agent is 20%; the cross-linking agent is N,N'-methylenebisacrylamide, and the mass of the cross-linking agent is 0.5% of the mass of the first main agent; the retarder is potassium ferrocyanide, and the mass of the retarder is 1% of the mass of the first main agent; the accelerator is triethanolamine, and the mass of the accelerator is 1% of the mass of the first main agent.

[0083] S2. Prepare the second component, including: adding an initiator to the second main agent and mixing them evenly; wherein the second main agent is an aqueous solution of a second acrylate, the second acrylate is the same as the first acrylate, and the mass fraction of the second acrylate in the second main agent is equal to the mass fraction of the first acrylate in the first main agent; the initiator is ammonium persulfate, and the mass of the initiator is 1% of the mass of the second main agent.

[0084] S3. preparing an acidic sodium silicate solution, comprising:

[0085] S31. Mixing sodium silicate with water to obtain a sodium silicate solution; wherein the modulus of the sodium silicate is 3.0; the Baume degree of the sodium silicate solution is 15Be°; and

[0086] S32. Slowly add the sodium silicate solution into the sulfuric acid solution and adjust the pH to 3 to obtain; wherein the mass fraction of sulfuric acid in the sulfuric acid solution is 5%.

[0087] It should be noted that the purpose of the above S1 to S3 is only to prepare the first component, the second component and the acidic sodium silicate solution respectively. This embodiment does not limit the execution order of the above S1 to S3, that is, this embodiment does not limit the order of preparing the first component, the second component and the acidic sodium silicate solution.

[0088] S4. Preparing a composite anti-seepage material, comprising:

[0089] S41. The first component is mixed with an acidic sodium silicate solution to obtain a mixed solution; wherein the volume ratio of the first component to the acidic sodium silicate solution is 1:1; and

[0090] S42. Mix the second component with the mixed solution to obtain; wherein the volume ratio of the first component, the second component and the acidic sodium silicate solution is 1:1:1.

[0091] Example 2

[0092] A method for preparing a composite anti-seepage material, comprising S1 to S4.

[0093] S1. Prepare the first component, including: adding a cross-linking agent, a retarder and an accelerator to the first main agent, and mixing them evenly to obtain; wherein the first main agent is an aqueous solution of a first acrylate, the first acrylate is magnesium acrylate and calcium acrylate in a mass ratio of 7:3, and the mass fraction of the first acrylate in the first main agent is 30%; the cross-linking agent is N,N'-methylenebisacrylamide, and the mass of the cross-linking agent is 5% of the mass of the first main agent; the retarder is potassium ferrocyanide, and the mass of the retarder is 2% of the mass of the first main agent; the accelerator is triethanolamine, and the mass of the accelerator is 0.1% of the mass of the first main agent.

[0094] S2. Prepare the second component, including: adding an initiator to the second main agent and mixing them evenly; wherein the second main agent is an aqueous solution of a second acrylate, the second acrylate is the same as the first acrylate, and the mass fraction of the second acrylate in the second main agent is equal to the mass fraction of the first acrylate in the first main agent; the initiator is ammonium persulfate, and the mass of the initiator is 0.1% of the mass of the second main agent.

[0095] S3. preparing an acidic sodium silicate solution, comprising:

[0096] S31. Mixing sodium silicate with water to obtain a sodium silicate solution; wherein the modulus of the sodium silicate is 2.6; the Baume degree of the sodium silicate solution is 10Be°; and

[0097] S32. Slowly add the sodium silicate solution into the sulfuric acid solution and adjust the pH to 2 to obtain; wherein the mass fraction of sulfuric acid in the sulfuric acid solution is 15%.

[0098] It should be noted that the purpose of the above S1 to S3 is only to prepare the first component, the second component and the acidic sodium silicate solution respectively. This embodiment does not limit the execution order of the above S1 to S3, that is, this embodiment does not limit the order of preparing the first component, the second component and the acidic sodium silicate solution.

[0099] S4. Preparing a composite anti-seepage material, comprising:

[0100] S41. mixing the first component with an acidic sodium silicate solution to obtain a mixed solution; and

[0101] S42. Mix the second component with the mixed solution to obtain; wherein the volume ratio of the first component, the second component and the acidic sodium silicate solution is 1:1:0.5.

[0102] Example 3

[0103] A method for preparing a composite anti-seepage material, which differs from the method for preparing a composite anti-seepage material provided in Example 2 in that:

[0104] The pH of the acidic sodium silicate solution is 4 (i.e., in S32, the pH is adjusted to 4);

[0105] Other conditions such as the selection and dosage of reagents and the steps and parameters of the method are the same as those in Example 2 of the present disclosure.

[0106] Example 4

[0107] A method for preparing a composite anti-seepage material, comprising S1 to S4.

[0108] S1. Prepare the first component, including: adding a cross-linking agent, a retarder and an accelerator to the first main agent, and mixing them evenly to obtain; wherein the first main agent is an aqueous solution of a first acrylate, the first acrylate is magnesium acrylate, and the mass fraction of the first acrylate in the first main agent is 10%; the cross-linking agent is divinylbenzene, and the mass of the cross-linking agent is 1% of the mass of the first main agent; the retarder is potassium ferrocyanide, and the mass of the retarder is 0.1% of the mass of the first main agent; the accelerator is triethanolamine, and the mass of the accelerator is 5% of the mass of the first main agent.

[0109] S2. Prepare the second component, including: adding an initiator to the second main agent and mixing them evenly; wherein the second main agent is an aqueous solution of a second acrylate, the second acrylate is the same as the first acrylate, and the mass fraction of the second acrylate in the second main agent is equal to the mass fraction of the first acrylate in the first main agent; the initiator is ammonium persulfate, and the mass of the initiator is 5% of the mass of the second main agent.

[0110] S3. preparing an acidic sodium silicate solution, comprising:

[0111] S31. Mixing sodium silicate with water to obtain a sodium silicate solution; wherein the modulus of the sodium silicate is 3.3; the Baume degree of the sodium silicate solution is 25Be°; and

[0112] S32. Slowly add the sodium silicate solution into the sulfuric acid solution and adjust the pH to 4 to obtain; wherein the mass fraction of sulfuric acid in the sulfuric acid solution is 10%.

[0113] It should be noted that the purpose of the above S1 to S3 is only to prepare the first component, the second component and the acidic sodium silicate solution respectively. This embodiment does not limit the execution order of the above S1 to S3, that is, this embodiment does not limit the order of preparing the first component, the second component and the acidic sodium silicate solution.

[0114] S4. Preparing a composite anti-seepage material, comprising:

[0115] S41. mixing the first component with an acidic sodium silicate solution to obtain a mixed solution; and

[0116] S42. Mix the second component with the mixed solution to obtain; wherein the volume ratio of the first component, the second component and the acidic sodium silicate solution is 1:2:4.

[0117] Example 5

[0118] A method for preparing a composite anti-seepage material, comprising S1 to S4.

[0119] S1. Prepare the first component, including: adding a cross-linking agent, a retarder and an accelerator to the first main agent, and mixing them evenly to obtain; wherein the first main agent is an aqueous solution of a first acrylate, the first acrylate is magnesium acrylate, and the mass fraction of the first acrylate in the first main agent is 40%; the cross-linking agent is pentaerythritol diacrylate, and the mass of the cross-linking agent is 2% of the mass of the first main agent; the retarder is potassium ferrocyanide, and the mass of the retarder is 1% of the mass of the first main agent; the accelerator is triethanolamine, and the mass of the accelerator is 2% of the mass of the first main agent.

[0120] S2. Prepare the second component, including: adding an initiator to the second main agent and mixing them evenly; wherein the second main agent is an aqueous solution of a second acrylate, the second acrylate is the same as the first acrylate, and the mass fraction of the second acrylate in the second main agent is equal to the mass fraction of the first acrylate in the first main agent; the initiator is ammonium persulfate, and the mass of the initiator is 2% of the mass of the second main agent.

[0121] S3. preparing an acidic sodium silicate solution, comprising:

[0122] S31. Mixing sodium silicate with water to obtain a sodium silicate solution; wherein the modulus of the sodium silicate is 3.0; the Baume degree of the sodium silicate solution is 15Be°; and

[0123] S32. Slowly add the sodium silicate solution into the sulfuric acid solution and adjust the pH to 2 to obtain; wherein the mass fraction of sulfuric acid in the sulfuric acid solution is 5%.

[0124] It should be noted that the purpose of the above S1 to S3 is only to prepare the first component, the second component and the acidic sodium silicate solution respectively. This embodiment does not limit the execution order of the above S1 to S3, that is, this embodiment does not limit the order of preparing the first component, the second component and the acidic sodium silicate solution.

[0125] S4. Preparing a composite anti-seepage material, comprising:

[0126] S41. mixing the first component with an acidic sodium silicate solution to obtain a mixed solution; and

[0127] S42. Mix the second component with the mixed solution to obtain; wherein the volume ratio of the first component, the second component and the acidic sodium silicate solution is 1:0.5:1.

[0128] Example 6

[0129] A method for preparing a composite anti-seepage material, comprising S1 to S4.

[0130] S1. Prepare the first component, including: adding a cross-linking agent, a retarder and an accelerator to the first main agent, and mixing them evenly to obtain; wherein the first main agent is an aqueous solution of a first acrylate, the first acrylate is magnesium acrylate, and the mass fraction of the first acrylate in the first main agent is 30%; the cross-linking agent is a diisocyanate, and the mass of the cross-linking agent is 2% of the mass of the first main agent; the retarder is potassium ferrocyanide, and the mass of the retarder is 1% of the mass of the first main agent; the accelerator is triethanolamine, and the mass of the accelerator is 2% of the mass of the first main agent.

[0131] S2. Prepare the second component, including: adding an initiator to the second main agent and mixing them evenly; wherein the second main agent is an aqueous solution of a second acrylate, the second acrylate is the same as the first acrylate, and the mass fraction of the second acrylate in the second main agent is equal to the mass fraction of the first acrylate in the first main agent; the initiator is ammonium persulfate, and the mass of the initiator is 2% of the mass of the second main agent.

[0132] S3. preparing an acidic sodium silicate solution, comprising:

[0133] S31. Mixing sodium silicate with water to obtain a sodium silicate solution; wherein the modulus of the sodium silicate is 3.0; the Baume degree of the sodium silicate solution is 15Be°; and

[0134] S32. Slowly add the sodium silicate solution into the sulfuric acid solution and adjust the pH to 2 to obtain; wherein the mass fraction of sulfuric acid in the sulfuric acid solution is 5%.

[0135] It should be noted that the purpose of the above S1 to S3 is only to prepare the first component, the second component and the acidic sodium silicate solution respectively. This embodiment does not limit the execution order of the above S1 to S3, that is, this embodiment does not limit the order of preparing the first component, the second component and the acidic sodium silicate solution.

[0136] S4. Preparing a composite anti-seepage material, comprising:

[0137] S41. mixing the first component with an acidic sodium silicate solution to obtain a mixed solution; and

[0138] S42. Mix the second component with the mixed solution to obtain; wherein the volume ratio of the first component, the second component and the acidic sodium silicate solution is 1:1:1.

[0139] Example 7

[0140] A method for preparing a composite anti-seepage material, comprising S1 to S4.

[0141] S1. Prepare the first component, including: adding a cross-linking agent, a retarder and an accelerator to the first main agent, and mixing them evenly to obtain; wherein the first main agent is an aqueous solution of a first acrylate, the first acrylate is calcium acrylate, and the mass fraction of the first acrylate in the first main agent is 30%; the cross-linking agent is ethylene glycol diacrylate, and the mass of the cross-linking agent is 2% of the mass of the first main agent; the retarder is potassium ferrocyanide, and the mass of the retarder is 1% of the mass of the first main agent; the accelerator is sodium bisulfite, and the mass of the accelerator is 2% of the mass of the first main agent.

[0142] S2. Prepare the second component, including: adding an initiator to the second main agent and mixing them evenly; wherein the second main agent is an aqueous solution of a second acrylate, the second acrylate is the same as the first acrylate, and the mass fraction of the second acrylate in the second main agent is equal to the mass fraction of the first acrylate in the first main agent; the initiator is sodium persulfate, and the mass of the initiator is 2% of the mass of the second main agent.

[0143] S3. preparing an acidic sodium silicate solution, comprising:

[0144] S31. Mixing sodium silicate with water to obtain a sodium silicate solution; wherein the modulus of the sodium silicate is 3.0; the Baume degree of the sodium silicate solution is 15Be°; and

[0145] S32. Slowly add the sodium silicate solution into the sulfuric acid solution and adjust the pH to 2 to obtain; wherein the mass fraction of sulfuric acid in the sulfuric acid solution is 5%.

[0146] It should be noted that the purpose of the above S1 to S3 is only to prepare the first component, the second component and the acidic sodium silicate solution respectively. This embodiment does not limit the execution order of the above S1 to S3, that is, this embodiment does not limit the order of preparing the first component, the second component and the acidic sodium silicate solution.

[0147] S4. Preparing a composite anti-seepage material, comprising:

[0148] S41. mixing the first component with an acidic sodium silicate solution to obtain a mixed solution; and

[0149] S42. Mix the second component with the mixed solution to obtain; wherein the volume ratio of the first component, the second component and the acidic sodium silicate solution is 1:1:2.

[0150] Comparative Example 1

[0151] The embodiment 1 of the present disclosure is compared with the comparative example 1, wherein the difference between the comparative example 1 and the embodiment 1 is:

[0152] The first component does not include a retarder (that is, when preparing the first component, a cross-linking agent and an accelerator are added to the first main agent and mixed evenly to obtain the first component);

[0153] Other conditions such as the selection and dosage of reagents and the steps and parameters of the method are the same as those in Example 1 of the present disclosure (compared with Example 1, no retarder was added in this control example, which is used to prove that the composite anti-seepage material prepared by the preparation method of the present disclosure has better effect).

[0154] Comparative Example 2

[0155] The embodiment 1 of the present disclosure is compared with the comparative example 2, wherein the difference between the comparative example 2 and the embodiment 1 is:

[0156] The composite anti-seepage material does not include acidic sodium silicate (that is, when preparing the composite anti-seepage material, the first component and the second component are mixed to obtain the composite anti-seepage material);

[0157] Other conditions such as the selection and dosage of reagents, as well as the steps and parameters of the method, are the same as those in Example 1 of the present disclosure (compared with Example 1, this control example does not add acidic sodium silicate, which is used to prove that the composite anti-seepage material prepared by the preparation method of the present disclosure has better effect).

[0158] Comparative Example 3

[0159] The embodiment 1 of the present disclosure is compared with the comparative example 3, wherein the difference between the comparative example 3 and the embodiment 1 is:

[0160] 1) The first component does not include a retarder (that is, when preparing the first component, a crosslinking agent and an accelerator are added to the first main agent and mixed evenly to obtain the first component);

[0161] 2) The composite anti-seepage material does not include acidic sodium silicate (that is, when preparing the composite anti-seepage material, the first component and the second component are mixed to obtain the composite anti-seepage material);

[0162] Other conditions such as the selection and dosage of reagents and the steps and parameters of the method are the same as those in Example 1 of the present disclosure (compared with Example 1, this control example did not add retarder and acidic sodium silicate, which is used to prove that the composite anti-seepage material prepared by the preparation method of the present disclosure has better effect).

[0163] Comparative Example 4

[0164] The embodiments 2 to 3 of the present disclosure are compared with the comparative example 4, wherein the difference between the comparative example 4 and the embodiments 2 to 3 is:

[0165] The pH of the acidic sodium silicate solution is 1.5 (i.e., in S32, the pH is adjusted to 1.5);

[0166] Other conditions such as the selection and dosage of reagents, as well as the steps and parameters of the method, are the same as those of Examples 2 to 3 of the present disclosure (the pH of the acidic sodium silicate solution in this control example is too low compared to Examples 2 to 3, which is used to prove that the composite anti-seepage material prepared by the preparation method of the present disclosure has better effect).

[0167] Comparative Example 5

[0168] Examples 2 to 3 of the present disclosure are compared with reference example 5, wherein the difference between reference example 5 and examples 2 to 3 is:

[0169] The pH of the acidic sodium silicate solution is 4.5 (i.e., in S32, the pH is adjusted to 4.5);

[0170] Other conditions such as the selection and dosage of reagents, as well as the steps and parameters of the method, are the same as those of Examples 2 to 3 of the present disclosure (the pH of the acidic sodium silicate solution in this control example is too high compared to Examples 2 to 3, which is used to prove that the composite anti-seepage material prepared by the preparation method of the present disclosure has better effect).

[0171] Comparative Example 6

[0172] Example 5 of the present disclosure is compared with reference example 6, wherein the difference between reference example 6 and example 5 is:

[0173] The first component does not include the first main agent (that is, when preparing the first component, the cross-linking agent, the retarder and the accelerator are uniformly mixed to obtain the first main agent);

[0174] Other conditions such as the selection and dosage of reagents and the steps and parameters of the method are the same as those in Example 5 of the present disclosure (compared with Example 5, this control example does not add the first acrylate, which is used to prove that the composite anti-seepage material prepared by the preparation method of the present disclosure has better effect).

[0175] Comparative Example 7

[0176] Example 5 of the present disclosure is compared with reference example 7, wherein the difference between reference example 7 and example 5 is:

[0177] The composite anti-seepage material does not include acidic sodium silicate (that is, when preparing the composite anti-seepage material, the first component and the second component are mixed to obtain the composite anti-seepage material);

[0178] Other conditions such as the selection and dosage of reagents and the steps and parameters of the method are the same as those in Example 5 of the present disclosure (compared with Example 5, this control example does not add acidic sodium silicate, which is used to prove that the composite anti-seepage material prepared by the preparation method of the present disclosure has better effect).

[0179] Experimental results

[0180] In order to verify the effect of the preparation method of the composite anti-seepage material provided in the present invention, the gelation time, permeability coefficient, compressive strength of the sand-solidifying body, water expansion rate and volume shrinkage rate of the anti-seepage materials prepared according to the preparation methods in Examples 1 to 7 and Control Examples 1 to 7 were tested respectively.

[0181] The results are shown in the following table:

[0182] Group Gel time / min <![CDATA[Coefficient of permeability / cm·s -1 > 7d compressive strength of sand consolidation / MPa Water expansion rate / % Volume shrinkage / % Example 1 24 <![CDATA[6.14×10 -8 ]]> 0.56 8 12 Comparative Example 1 8 <![CDATA[6.34×10 -8 ]]> 0.55 9 11 Comparative Example 2 9 <![CDATA[6.78×10 -8 ]]> 0.61 45 61 Comparative Example 3 1 <![CDATA[6.58×10 -8 ]]> 0.60 47 66 Example 2 38 <![CDATA[6.78×10 -8 ]]> 0.48 15 20 Example 3 25 <![CDATA[6.28×10 -8 ]]> 0.47 16 21 Comparative Example 4 185 <![CDATA[6.88×10 -8 ]]> 0.45 11 18 Comparative Example 5 2 <![CDATA[6.38×10 -8 ]]> 0.46 13 19 Example 4 9 <![CDATA[3.24×10 -8 ]]> 0.21 4 5 Example 5 29 <![CDATA[8.89×10 -8 ]]> 0.62 12 16 Comparative Example 6 125 <![CDATA[5.66×10 -7 ]]> 0.11 3 4 Comparative Example 7 8 <![CDATA[7.89×10 -8 ]]> 0.65 47 68 Example 6 34 <![CDATA[7.14×10 -8 ]]> 0.56 6 9 Example 7 32 <![CDATA[6.47×10 -8 ]]> 0.43 6 8

[0183] It can be seen from the above table:

[0184] 1) The anti-seepage materials obtained by the preparation methods of Examples 1 to 7 have a gelation time in the range of 9 to 38 min and a permeability coefficient in the range of 3.24×10 -8 ~8.89×10 -8 cm·s -1 The compressive strength of the sand-solidifying body is within the range of 0.21-0.62MPa, the water expansion rate is within the range of 4%-16%, and the volume shrinkage rate is within the range of 5%-21%. It can be seen that the gelling time, permeability coefficient, compressive strength of the sand-solidifying body, water expansion rate and volume shrinkage rate of the anti-seepage material obtained by the preparation method of Examples 1-7 are all in an excellent range, which shows that the preparation method provided by the present disclosure at least achieves the effects of controllable gelling time, good anti-seepage effect, high compressive strength and small volume phase change.

[0185] 2) The gelling time of the anti-seepage material obtained by the preparation method of Reference Example 3 is too short, specifically 1 min; compared with the anti-seepage material obtained by the preparation method of Reference Example 3, the gelling time of the anti-seepage material obtained by the preparation method of Reference Example 1 is slowed down by 7 min, the gelling time of the anti-seepage material obtained by the preparation method of Reference Example 2 is slowed down by 8 min, and the gelling time of the anti-seepage material obtained by the preparation method of Example 1 is slowed down by 23 min; it can be seen that, compared with the anti-seepage material obtained by the preparation method of Reference Example 3, the degree of improvement in the ability to regulate the gelling time of the anti-seepage material obtained by the preparation method of Example 1 is greater than the sum of the degrees of improvement in the ability to regulate the gelling time of the anti-seepage material obtained by the preparation method of Reference Example 1 and the anti-seepage material obtained by the preparation method of Reference Example 2, that is, 7+8<23, which shows that in the preparation method provided by the present disclosure, the retarder and the acidic sodium silicate have a synergistic effect on regulating the gelling time of the anti-seepage material;

[0186] 3) The gelling time of the anti-seepage material obtained by the preparation method of Control Example 4 is too long, which is 185 min. Compared with the anti-seepage material obtained by the preparation method of Control Example 4, the gelling time of the anti-seepage material obtained by the preparation method of Example 2 is accelerated by 147 min. The gelling time of the anti-seepage material obtained by the preparation method of Control Example 5 is too short, which is 2 min. Compared with the anti-seepage material obtained by the preparation method of Control Example 5, the gelling time of the anti-seepage material obtained by the preparation method of Example 3 is slowed down by 23 min. This shows that in the preparation method provided by the present disclosure, the ability of the anti-seepage material to regulate the gelling time can be improved by limiting the pH of the acidic sodium silicate.

[0187] 4) Compared with the anti-seepage material obtained by the preparation method of Example 5, the gelling time of the anti-seepage material obtained by the preparation method of Control Example 6 is too long and the compressive strength of the solid sand body is significantly reduced, and the gelling time of the anti-seepage material obtained by the preparation method of Control Example 7 is too short and the water expansion rate and volume shrinkage rate are significantly increased. This shows that in the preparation method provided in the present disclosure, acidic sodium silicate and acrylate have a synergistic effect in regulating the gelling time, compressive strength and volume phase change of the composite anti-seepage material.

[0188] Therefore, the preparation method of a composite anti-seepage material, its product and application provided by the present disclosure at least achieve the characteristics of simple preparation method, high compressive strength, high later stability, good anti-seepage effect, good durability, uniform liquid, environmental friendliness and low cost, and can be applied to the anti-seepage effect of ionic rare earth mines.

[0189] The above is only a preferred embodiment of the present disclosure. It should be understood that the present disclosure is not limited to the form disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the concept described herein through the above teachings or the technology or knowledge of the relevant field. The changes and modifications made by those skilled in the art do not deviate from the spirit and scope of the present disclosure, and should be within the scope of protection of the claims attached to the present disclosure.

Claims

1. A method for preparing a composite anti-seepage material, characterized in that: include: mixing the first component with an acidic sodium silicate solution to obtain a mixed solution; as well as Mixing the second component with the mixed liquid to obtain the composite anti-seepage material; The pH of the acidic sodium silicate solution is 2-4; the first component includes a first main agent, a cross-linking agent, a retarder and an accelerator; the first main agent includes an aqueous solution of a first acrylate, and the first acrylate includes at least one of calcium acrylate and magnesium acrylate; the retarder includes potassium ferrocyanide; The second component includes an initiator; the initiator includes at least one of ammonium persulfate and sodium persulfate; The volume ratio of the first component, the second component and the acidic sodium silicate solution is 1:0.5-2:0.5-4; The second component also includes a second main agent; the second main agent includes an aqueous solution of a second acrylate, and the second acrylate is the same as the first acrylate; The method for preparing the acidic sodium silicate solution comprises: mixing sodium silicate with water to obtain a sodium silicate solution; and Mixing the sulfuric acid solution with the sodium silicate solution to obtain the acidic sodium silicate solution; Wherein, the modulus of the sodium silicate is 2.6~3.3; The Baume degree of the sodium silicate solution is 10-25 Be°; The mass fraction of sulfuric acid in the sulfuric acid solution is 5% to 15%.

2. The preparation method according to claim 1, characterized in that: The mass fraction of the first acrylate in the first main agent is 10% to 40%.

3. The preparation method according to claim 1, characterized in that: The mass fraction of the second acrylate in the second main agent is equal to the mass fraction of the first acrylate in the first main agent; And / or, the mass of the initiator is 0.1% to 5% of the mass of the second main agent.

4. The preparation method according to claim 1, characterized in that: The crosslinking agent includes at least one of N,N'-methylenebisacrylamide, ethylene glycol diacrylate, pentaerythritol diacrylate, divinylbenzene and diisocyanate; And / or, the promoter includes at least one of triethanolamine and sodium bisulfite.

5. The preparation method according to claim 1 or 4, characterized in that: The mass of the cross-linking agent is 0.5% to 5% of the mass of the first main agent; And / or, the mass of the retarder is 0.1% to 2% of the mass of the first main agent; And / or, the mass of the accelerator is 0.1% to 5% of the mass of the first main agent.

6. A composite anti-seepage material, characterized in that: The method is prepared according to any one of claims 1 to 5.

7. Use of the preparation method according to any one of claims 1 to 5 or the composite anti-seepage material according to claim 6 in the anti-seepage of ionic rare earth mines.