High-porosity gangue-based carbon sequestration filling and grouting material, preparation method and application

Abstract

The application provides a high-porosity gangue-based carbon fixation filling grouting material, a preparation method and application thereof. The high-porosity gangue-based carbon fixation filling grouting material comprises, in parts by weight, 50-80 parts of coal gangue powder, 10-30 parts of magnesium slag powder, 5-20 parts of superabsorbent resin monomer, 0-5 parts of carbide slag powder, 0.05-0.3 parts of a crosslinking agent, 0.1-0.5 parts of an initiator, 0.1-0.6 parts of a foaming agent, 0.1-0.3 parts of a foam stabilizer, 60-100 parts of water and 2-10 parts of CO2. By adjusting the ratio of the superabsorbent resin monomer and the initiator, the material is coagulated within 15-100 min, the early entering bubbles in the slurry are prevented from breaking and overflowing, chemical carbon fixation and more efficient CO2 geological sequestration are achieved through the reaction of the magnesium slag, the carbide slag and the CO2, the slurry finally forms a high-porosity structure through the control of the ratio and the reaction conditions, the cost of the filling material is effectively reduced, and the high-porosity gangue-based carbon fixation filling grouting material can be applied to different operation scenes such as filling mining and roof grouting.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of grouting materials, and particularly relates to a high-porosity gangue-based carbon fixation filling grouting material, a preparation method and application. BACKGROUND

[0002] At present, the following problems are mainly faced in the popularization of filling mining technology in China: the long condensation time of filling materials causes the hydraulic support to be unable to move in time, so that the filling operation affects the coal mining speed and further affects the coal production benefit; the quantity of gangue, a main filling material required for large-scale filling mining, is seriously insufficient; the filling operation cost is too high to meet the requirements of low-carbon, zero-carbon and negative-carbon green mining. The above technical problems can be solved by the following ways: shortening the condensation time of filling materials; replacing the conventional filling materials with high-porosity filling materials; and using the grouting material containing materials capable of adsorbing, combining and solidifying carbon dioxide. A large amount of industrial CO2 waste gas needs to be treated, and coal gangue, magnesium slag, calcium carbide slag and other solid waste materials in many regions also need to be treated and utilized.

[0003] In summary, using magnesium slag, calcium carbide slag and other materials as glue materials, coal gangue as base material, and introducing CO2 for carbonization activation to make them have cementitious activity, and then preparing filling grouting materials is a good way, which can be used for mine filling mining and coal mine roof grouting in different scenes. SUMMARY

[0004] In view of the deficiencies of the prior art, the purpose of the application is to provide a high-porosity gangue-based carbon fixation filling grouting material, a preparation method and application. The high-porosity gangue-based carbon fixation filling grouting material uses solid waste as the main raw material, is suitable for different scenes such as filling mining and coal mine roof grouting, can combine and solidify a large amount of CO2, and can realize CO2 geological storage when the carbon fixation filling grouting material is used for goaf filling.

[0005] In order to solve the above technical problems, the application adopts the following technical scheme:

[0006] A high-porosity gangue-based carbon fixation filling grouting material, by weight fraction, comprises the following raw material components: coal gangue micro powder 50-80 parts, magnesium slag micro powder 10-30 parts, high water absorption resin monomer 5-20 parts, calcium carbide slag micro powder 0-5 parts, crosslinking agent 0.05-0.3 parts, initiator 0.1-0.5 parts, foaming agent 0.1-0.6 parts, foam stabilizer 0.1-0.3 parts, water 60-100 parts and CO2 2-10 parts.

[0007] The application also has the following technical features:

[0008] Specifically, the coal gangue micro-powder has a particle size less than 100 mesh, the magnesium slag micro-powder has a particle size less than 200 mesh, and the carbide slag micro-powder has a particle size less than 200 mesh.

[0009] Further, the high water-absorbing resin monomer comprises an acrylamide monomer.

[0010] Further, the cross-linking agent comprises N,N-methylene bisacrylamide.

[0011] Further, the initiator comprises industrial-grade ammonium persulfate and potassium persulfate.

[0012] Further, the foaming agent comprises sodium dodecyl sulfate, protein foaming agent, cocobutyl propyl amide betaine and sodium alkenyl sulfonate.

[0013] Further, the foam stabilizer is compounded by 30-40% calcium stearate and 60-70% sodium dodecyl benzene sulfonate.

[0014] The application also protects a preparation method of the high-pore gangue-based carbon sequestration filling and grouting material, comprising the following steps:

[0015] Step 1, mix the coal gangue micro-powder with a particle size less than 100 mesh and the magnesium slag micro-powder with a particle size less than 200 mesh at a speed of 50-100 r / min for 3-5 min to obtain a mixed material A; mix the mixed material A with water at a speed of 100-200 r / min for 3-5 min to obtain a slurry B;

[0016] Step 2, add the formula amount of the high water-absorbing resin monomer, the cross-linking agent and the initiator into the slurry B in sequence, and mix and stir at a speed of 100-200 r / min for 3-5 min to obtain a slurry C;

[0017] Step 3, add the formula amount of the foaming agent and the foam stabilizer into the slurry C, mix and stir at a speed of 200-300 r / min for 10-30 min, and continuously introduce the industrial waste gas with a carbon dioxide content of 10-20% into the slurry C at a ventilation rate of 1-3 mL / min / g during the stirring process to obtain a slurry D;

[0018] Step 4, add the carbide slag micro-powder with a particle size less than 200 mesh into the slurry D, and mix and stir at a speed of 100-200 r / min for 1-3 min to obtain the high-pore gangue-based carbon sequestration filling and grouting material.

[0019] By weight parts, coal gangue micro powder 50-80 parts, magnesium slag micro powder 10-30 parts, high water absorption resin monomer 5-20 parts, carbide slag micro powder 0-5 parts, crosslinking agent 0.05-0.3 parts, initiator 0.1-0.5 parts, foaming agent 0.1-0.6 parts, foam stabilizer 0.1-0.3 parts, water 60-100 parts and CO2 2-10 parts.

[0020] Optionally, specifically comprising the following steps:

[0021] Step 1, the particle size of less than 100 mesh coal gangue micro powder and particle size of less than 200 mesh magnesium slag micro powder are mixed and stirred at a speed of 50 r / min for 3 min, to obtain a mixed material A; the mixed material A is mixed with water, and mixed and stirred at a speed of 100 r / min for 5 min, to obtain a slurry B;

[0022] Step 2, the formula amount of high water absorption resin monomer, crosslinking agent and initiator are sequentially added to the slurry B, and mixed and stirred at a speed of 200 r / min for 3 min, to obtain a slurry C;

[0023] Step 3, the formula amount of foaming agent and foam stabilizer is added to the slurry C, and mixed and stirred at a speed of 300 r / min for 20 min, and the industrial waste gas with a carbon dioxide content of 10-20% is continuously introduced in the stirring process, and the aeration rate is 3 mL / min / g, to obtain a slurry D;

[0024] Step 4, the particle size of less than 200 mesh carbide slag micro powder is added to the slurry D, and mixed and stirred at a speed of 200 r / min for 2 min, to obtain a slurry E;

[0025] Wherein, by weight parts, coal gangue micro powder 50 parts, magnesium slag micro powder 30 parts, high water absorption resin monomer 20 parts, carbide slag micro powder 5 parts, crosslinking agent 0.2 parts, initiator 0.4 parts, foaming agent 0.3 parts, foam stabilizer 0.1 parts, water 90 parts and CO2 6 parts.

[0026] The application also protects the application of the above high-porosity gangue-based carbon sequestration filling grouting material for filling mining.

[0027] Compared with the prior art, the application has the following technical effects:

[0028] (I) The method of the application uses a large amount of solid waste and industrial waste gas, adjusts the ratio of high water absorption resin monomer and initiator, and makes the material coagulate within 15-100 min, which does not affect the coal mining speed during the filling operation, ensures that the bubbles in the slurry do not break and overflow, realizes chemical carbon sequestration and more efficient CO2 geological sequestration through the reaction of magnesium slag, carbide slag and CO2, and finally forms a high-porosity structure through control of the ratio and reaction conditions, effectively reducing the cost of the filling material.

[0029] (2) The high-porosity gangue-based carbon sequestration filling and grouting material provided by the present application has low cost, can initial set and final set in a short time, utilizes the characteristics of different components to achieve the technical effects of taking advantage of each other's strengths, synergistic activation, waste treatment, and waste-to-resource.

[0030] (3) The component ratio of the high-porosity gangue-based carbon sequestration filling and grouting material provided by the present application can be adjusted according to actual needs on site, and by changing the composition and ratio of raw materials, the material can be matched with different grouting processes and can be applied to different operation scenarios such as filling mining and roof grouting. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 The XRD phase comparison chart of the high-porosity gangue-based carbon sequestration filling and grouting material prepared for Example 1 and Comparative Example 1 is shown in the following figure;

[0032] Figure 2 The infrared spectrum comparison chart of the high-porosity gangue-based carbon sequestration filling and grouting material prepared for Example 1 and Comparative Example 1 is shown in the following figure;

[0033] Figure 3 The micrometer-scale microstructure morphology chart of the high-porosity gangue-based carbon sequestration filling and grouting material prepared for Example 1 is shown in the following figure;

[0034] Figure 4 The micrometer-scale microstructure morphology chart of the high-porosity gangue-based carbon sequestration filling and grouting material prepared for Example 1 is shown in the following figure;

[0035] The specific content of the present application will be further described in detail below in combination with the drawings and examples. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present application will be clearly and completely described below. 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, any other embodiments obtained by any person of ordinary skill in the art belong to the scope of protection of the present application.

[0037] It should be noted that all raw materials in the present application, unless otherwise specified, are known raw materials in the art.

[0038] The technical concept of the present application is that coal gangue, carbide slag, and magnesium slag all belong to different industrial solid wastes, and CO2 gas in industrial waste gas also needs to be treated. Coupling them together to form a material with cementitious properties to replace cement in traditional cemented filling materials not only treats solid waste but also promotes CO2 emission reduction, and at the same time provides filling materials for coal mine filling mining.

[0039] The main components of magnesium slag are γ-C2S, β-C2S, CaO and MgO, and the main component of carbide slag is Ca(OH)2. When the magnesium slag and the carbide slag meet CO2 in industrial waste gas, the following reactions occur respectively: C2S + 2CO2→ 2CaCO3 + SiO2(gel), CaO + CO2→ CaCO3, MgO + CO2→ MgCO3, Ca(OH)2 + CO2→ CaCO3 + H2O, SiO2(gel) + Ca(OH)2 + H2O→ C-S-H(gel). On the one hand, the carbonation reaction effectively absorbs and utilizes CO2; on the other hand, the generated CaCO3 provides nucleation sites for the reaction of SiO2(gel) and Ca(OH)2 in the system, accelerates the generation of C-S-H gel, and makes the slurry coagulate faster. That is, the carbonation reaction of CO2 makes the magnesium slag active, and the generated products increase the density of the system, and can further react with the carbide slag to generate a large amount of cementitious material, giving the rock body a high density. The increase of cementitious material in the whole system also makes the inactivated coal gangue powder and each part more firmly bonded, thereby increasing the strength of the material. The presence of the foaming agent and the foam stabilizer makes the initial foam of the slurry not easy to break. The addition of acrylamide, initiator and crosslinking agent enables the material to form a homogeneous high-porosity structure. The rapid coagulation reaction of acrylamide enables a large number of bubbles to be solidified in time, and the polyacrylamide gel generated by the reaction gives the pore wall toughness, so that the CO2 stored therein is not easy to overflow. At the same time, due to the low density, high strength, high stability, excellent fluidity, low drying shrinkage and other advantages of the high-porosity gangue-based carbon sequestration filling grouting material, it can be applied to different filling scenes.

[0040] In the present application, the requirements of each material used are as follows:

[0041] Coal gangue is a solid waste of coal mining. After crushing, grinding, and screening, the ground coal gangue powder is mainly used as a filler. Similar solid wastes include fly ash, slag, and gasification slag, etc.

[0042] The present application provides a high-porosity gangue-based carbon sequestration filling grouting material, which comprises the following raw material components in parts by weight: coal gangue powder 50-80 parts, magnesium slag powder 10-30 parts, superabsorbent resin monomer 5-20 parts, carbide slag powder 0-5 parts, crosslinking agent 0.05-0.3 parts, initiator 0.1-0.5 parts, foaming agent 0.1-0.6 parts, foam stabilizer 0.1-0.3 parts, water 60-100 parts and CO2 2-10 parts.

[0043] Preferably, the particle size of the coal gangue powder is less than 100 mesh, the particle size of the magnesium slag powder is less than 200 mesh, and the particle size of the carbide slag powder is less than 200 mesh.

[0044] As preferred, the high water-absorbing resin monomer comprises acrylamide monomer.

[0045] As preferred, the cross-linking agent comprises N,N-methylene bisacrylamide.

[0046] As preferred, the initiator comprises industrial-grade ammonium persulfate and potassium persulfate.

[0047] As preferred, the foaming agent comprises sodium dodecyl sulfate, protein foaming agent, cocobutyl amide betaine and sodium alkenyl sulfonate.

[0048] As preferred, the foam stabilizer is compounded by 30-40% calcium stearate and 60-70% sodium dodecyl benzene sulfonate surfactant.

[0049] The application also provides a preparation method of high-pore gangue-based carbon sequestration filling grouting material, comprising the following steps:

[0050] Step 1, mix and stir coal gangue powder with particle size less than 100 mesh and magnesium slag powder with particle size less than 200 mesh at a speed of 50-100 r / min for 3-5 min to obtain mixed material A; mix mixed material A with water at a speed of 100-200 r / min for 3-5 min to obtain slurry B;

[0051] Step 2, add formula amount of high water-absorbing resin monomer, cross-linking agent and initiator into slurry B in sequence, and mix and stir at a speed of 100-200 r / min for 3-5 min to obtain slurry C;

[0052] Step 3, add formula amount of foaming agent and foam stabilizer into slurry C, mix and stir at a speed of 200-300 r / min for 10-30 min, and continuously introduce industrial waste gas with carbon dioxide content of 10-20% into the stirring process at a ventilation rate of 1-3 mL / min / g to obtain slurry D;

[0053] Step 4, add calcium carbide slag powder with particle size less than 200 mesh into slurry D, and mix and stir at a speed of 100-200 r / min for 1-3 min to obtain the product.

[0054] Among them, the coal gangue powder is 50-80 parts, the magnesium slag powder is 10-30 parts, the high water-absorbing resin monomer is 5-20 parts, the calcium carbide slag powder is 0-5 parts, the cross-linking agent is 0.05-0.3 parts, the initiator is 0.1-0.5 parts, the foaming agent is 0.1-0.6 parts, the foam stabilizer is 0.1-0.3 parts, the water is 60-100 parts and CO2 is 6 parts.

[0055] The following gives specific embodiments of the present application, it is to be noted that the present application is not limited to the following specific embodiments, any equivalent transformation made on the basis of the technical solutions of the present application falls within the protection scope of the present application.

[0056] Embodiment 1

[0057] The present embodiment gives a preparation method of a high-pore gangue-based carbon sequestration filling grouting material, which specifically comprises the following steps:

[0058] Step 1, mix and stir coal gangue powder with particle size less than 100 mesh and magnesium slag powder with particle size less than 200 mesh at a speed of 50 r / min for 3 min to obtain mixed material A; mix mixed material A with water at a speed of 100 r / min for 5 min to obtain slurry B;

[0059] Step 2, add formula amount of superabsorbent resin monomer, crosslinking agent and initiator into slurry B in sequence, and mix and stir at a speed of 200 r / min for 3 min to obtain slurry C;

[0060] Step 3, add formula amount of foaming agent and foam stabilizer into slurry C, mix and stir at a speed of 300 r / min for 20 min, and continuously introduce industrial waste gas with carbon dioxide content of 10-20% at a rate of 3 mL / min / g in the stirring process, the aeration time is 20 min at a speed of 300 r / min, to obtain slurry D;

[0061] Step 4, add calcium carbide slag powder with particle size less than 200 mesh into slurry D, mix and stir at a speed of 100-200 r / min for 1-3 min to obtain the product.

[0062] Among them, the coal gangue powder is 50 parts, the magnesium slag powder is 30 parts, the superabsorbent resin monomer is 20 parts, the calcium carbide slag powder is 5 parts, the crosslinking agent is 0.2 parts, the initiator is 0.4 parts, the foaming agent is 0.3 parts, the foam stabilizer is 0.1 parts, the water is 90 parts, and the CO2 is 6 parts.

[0063] The high-pore gangue-based carbon sequestration filling grouting material prepared in the present embodiment is subjected to performance test, and the results are shown in Table 1.

[0064] The high-pore gangue-based carbon sequestration filling grouting material prepared in the present embodiment can be used for filling mining, and can also be used for other working conditions as needed, such as coal mine floor grouting, roof grouting and separation layer grouting.

[0065] Embodiment 2

[0066] The operation method steps in the present embodiment are the same as those in Embodiment 1.

[0067] The difference is that, in terms of parts by weight: 60 parts of coal gangue powder, 25 parts of magnesium slag powder, 15 parts of superabsorbent resin monomer, 4 parts of carbide slag powder, 0.15 parts of crosslinking agent, 0.3 parts of initiator, 0.5 parts of foaming agent, 0.2 parts of foam stabilizer, 80 parts of water, and the aeration rate of the captured industrial waste gas (CO2 content 10%~20%) is 3mL / min / g, and the aeration time is 20min at a rate of 300r / min.

[0068] The performance of the high-porosity gangue-based carbon sequestration filling and grouting material prepared in this example was tested, and the results are shown in Table 1.

[0069] Example 3

[0070] The operating method steps in this example are the same as those in Example 1.

[0071] The difference is that, in terms of parts by weight: 60 parts of coal gangue powder, 25 parts of magnesium slag powder, 15 parts of superabsorbent resin monomer, 4 parts of carbide slag powder, 0.15 parts of crosslinking agent, 0.3 parts of initiator, 0.5 parts of foaming agent, 0.2 parts of foam stabilizer, 80 parts of water, and the aeration rate of the captured industrial waste gas (CO2 content 10%~20%) is 3mL / min / g, and the aeration time is 20min at a rate of 300r / min.

[0072] The performance of the high-porosity gangue-based carbon sequestration filling and grouting material prepared in this example was tested, and the results are shown in Table 1.

[0073] Example 4

[0074] The operating method steps in this example are the same as those in Example 1.

[0075] The difference is that, in terms of parts by weight: 60 parts of coal gangue powder, 25 parts of magnesium slag powder, 15 parts of superabsorbent resin monomer, 4 parts of carbide slag powder, 0.15 parts of crosslinking agent, 0.3 parts of initiator, 0.5 parts of foaming agent, 0.2 parts of foam stabilizer, 80 parts of water, and the aeration rate of the captured industrial waste gas (CO2 content 10%~20%) is 3mL / min / g, and the aeration time is 20min at a rate of 300r / min.

[0076] The performance of the high-porosity gangue-based carbon sequestration filling and grouting material prepared in this example was tested, and the results are shown in Table 1.

[0077] Example 5

[0078] In this example, the dosages of coal gangue powder, magnesium slag powder, superabsorbent resin monomer, carbide slag powder, crosslinking agent, initiator, foaming agent, foam stabilizer, and water are the same as those in Example 1, and the operating method steps 1, 2, 3, and 5 are the same.

[0079] Different, the operation method step 3 is: the rubber tube of the gas bottle connected with industrial waste gas (CO2 content 10%~20%) is passed into the bottom of the stirring container, the ventilation rate is 1 mL / min / g, and the mixing stirring is carried out at the rate of 300 r / min for 20 min, and the foaming agent and the foam stabilizer are added.

[0080] The high-porosity gangue-based carbon sequestration filling and grouting material prepared in the example was tested for performance, and the results are shown in Table 1.

[0081] Example 6

[0082] In the example, the dosages of coal gangue micro powder, magnesium slag micro powder, superabsorbent resin monomer, carbide slag micro powder, crosslinking agent, initiator, foaming agent, foam stabilizer and water are the same as in Example 1, and the operation method steps 1, 2, 3 and 5 are the same.

[0083] Different, the operation method step 3 is: the rubber tube of the gas bottle connected with industrial waste gas (CO2 content 10%~20%) is passed into the bottom of the stirring container, the ventilation rate is 3 mL / min / g, and the mixing stirring is carried out at the rate of 200 r / min for 20 min, and the foaming agent and the foam stabilizer are added.

[0084] The high-porosity gangue-based carbon sequestration filling and grouting material prepared in the example was tested for performance, and the results are shown in Table 1.

[0085] Example 7

[0086] In the example, the dosages of coal gangue micro powder, magnesium slag micro powder, superabsorbent resin monomer, carbide slag micro powder, crosslinking agent, initiator, foaming agent, foam stabilizer and water are the same as in Example 1, and the operation method steps 1, 2, 3 and 5 are the same.

[0087] Different, the operation method step 3 is: the rubber tube of the gas bottle connected with industrial waste gas (CO2 content 10%~20%) is passed into the bottom of the stirring container, the ventilation rate is 3 mL / min / g, and the mixing stirring is carried out at the rate of 300 r / min for 10 min, and the foaming agent and the foam stabilizer are added.

[0088] The high-porosity gangue-based carbon sequestration filling and grouting material prepared in the example was tested for performance, and the results are shown in Table 1.

[0089] Comparative Example 1

[0090] In the example, the operation method steps are the same as in Example 1.

[0091] The difference is that, in parts by weight: coal gangue powder 50 parts, magnesium slag powder 30 parts, superabsorbent resin monomer 20 parts, carbide slag powder 3 parts, crosslinking agent 0.6 parts, initiator 0.3 parts, foaming agent 0.3 parts, foam stabilizer 0.1 parts, water 90 parts, and the captured industrial waste gas (after treatment, CO2 content 0%) is ventilated at a rate of 3 mL / min / g, and the ventilation time is 20 min at a rate of 300 r / min.

[0092] The high-porosity gangue-based carbon sequestration filling and grouting material prepared in the present comparative example was subjected to performance testing, and the results are shown in Table 1.

[0093] Comparative Example 2

[0094] The operation method steps in the present example are the same as those in Example 1.

[0095] The difference is that, in parts by weight: coal gangue powder 50 parts, magnesium slag powder 30 parts, superabsorbent resin monomer 20 parts, carbide slag powder 3 parts, crosslinking agent 0.6 parts, initiator 0.3 parts, foaming agent 0.3 parts, foam stabilizer 0.1 parts, water 90 parts, and the captured industrial waste gas (after treatment, CO2 content 0%) is ventilated at a rate of 3 mL / min / g, and the ventilation time is 20 min at a rate of 300 r / min.

[0096] The high-porosity gangue-based carbon sequestration filling and grouting material prepared in the present comparative example was subjected to performance testing, and the results are shown in Table 1.

[0097] Comparative Example 3

[0098] The present comparative example is a common industrial solid waste-based cementing grouting material on the market, and the industrial solid waste-based cementing grouting material comprises, in parts by weight: red mud 5 parts, desulfurization gypsum 6 parts, mineral powder 5 parts, coal gangue 30 parts, carbide slag 6 parts, aluminum powder 1 part, and water 47 parts.

[0099] In the present solution, the carbon sequestration rate is calculated using the following formula:

[0100]

[0101] wherein ω is the carbon sequestration rate;

[0102] w is the expansion ratio;

[0103] p is the percentage of CO2 in the industrial waste gas;

[0104] m x is the dried mass of the cured material, in kg;

[0105] m0 is the mass of the raw material, in kg;

[0106] p m is the water content of the raw material.

[0107] The test results obtained for Examples 1-7 and Comparative Examples 1-3 are shown in the following table:

[0108] Setting time / min Apparent density / (kg / m 3 )]]> Swelling ratio / times 7d compressive strength / MPa Carbon fixation rate / % Example 1 17 464 2.53 2.96 23.55 Example 2 25 472 2.41 2.73 21.60 Example 3 36 653 1.82 2.49 13.21 Example 4 52 754 1.67 2.24 10.45 Example 5 43 1362 1.37 1.37 4.94 Example 6 21 542 2.32 2.35 14.30 Example 7 27 631 1.89 1.62 8.58 Comparative Example 1 33 1452 1.13 1.21 0 Comparative Example 2 24 876 1.51 0.96 5.10 Comparative Example 3 286 630 1.89 1.9 0

[0109] Table 1, Test results of grouting materials in examples and comparative examples

[0110] Among them, the preparation process of Examples 1-4 is the same, the main change is the dosage of magnesium slag and superabsorbent resin monomer. From the test results of Examples 1-4, it can be seen that with the decrease of the dosage of magnesium slag, the carbon sequestration rate of the material is continuously reduced, because magnesium slag can absorb and solidify a large amount of CO2, and a large amount of active silica gel is generated after carbonation reaction, which not only solidifies carbon dioxide, but also improves the strength of the material. From Examples 1-4, it can be seen that the expansion ratio of the material is continuously decreasing, because with the decrease of the dosage of superabsorbent resin monomer, the setting time of the material gradually becomes longer, and some pores gradually collapse and rupture during the solidification process, ultimately leading to a decrease in the expansion ratio. In summary, the factors that have a greater impact on the performance of the grouting material are the dosages of magnesium slag and superabsorbent resin monomer.

[0111] The material ratio and preparation process of Examples 5-7 are the same as those of Example 1, the main difference is that the conditions for introducing industrial waste gas are changed. In Example 5, the gas flow rate is changed from 3 mL / min / g to 1 mL / min / g, and other conditions remain unchanged; in Example 6, the stirring speed is changed from 300 r / min to 200 r / min, and other conditions remain unchanged; in Example 7, the mixing and stirring time is changed from 20 min to 10 min, and other conditions remain unchanged.

[0112] From Example 5, it can be seen that when the gas flow rate of industrial waste gas is reduced, the expansion ratio, compressive strength and carbon sequestration rate of the material are all greatly reduced. This is because the reduction of the gas flow rate of industrial waste gas leads to a decrease in the CO2 content in the system, and a large amount of magnesium slag cannot be effectively activated, thus becoming a general filler without cementitious property, resulting in a decrease in material strength and a large number of pore ruptures, and CO2 cannot be effectively sequestered.

[0113] From Example 6, it can be seen that when the industrial waste gas is introduced, the stirring speed is changed from 300 r / min to 200 r / min, and the expansion ratio, compressive strength and carbon sequestration rate of the material are all reduced, because the reduction of the stirring speed also reduces the collision probability of magnesium slag and CO2 in the system, thus reducing the reaction degree of magnesium slag, leading to a decrease in the overall performance of the material.

[0114] It can be seen from Example 7 that after the industrial waste gas is introduced, the stirring time is changed from 20 min to 10 min, and the expansion ratio, compressive strength and carbon fixation rate of the material are all reduced, which is because the contact time of the material and CO2 in the system is reduced, so that the magnesium slag in the system is not fully carbonized and activated, and then the performance of the material is reduced. Examples 5-7 can show that the introduction conditions of industrial waste gas have a great influence on the performance of the material.

[0115] The material ratio and preparation process of Comparative Example 1 are the same as those of Example 1, except that the CO2 content in the industrial waste gas is changed to 0%, i.e., the raw material components used to prepare the grouting material do not contain CO2. From the test results, it can be seen that when the system does not contain CO2, the expansion ratio, compressive strength and carbon fixation rate of the material are greatly reduced, among which the expansion ratio is 1.13 and the carbon fixation rate is 0%. This is because without CO2 in the system, the magnesium slag and carbide slag cannot be carbonized and activated into cementitious materials, so they can only become inactive fillers, which further reduces the performance of the material.

[0116] The material preparation process and industrial waste gas introduction conditions of Comparative Example 2 are the same as those of Example 1, except that the amount of magnesium slag and carbide slag in the ratio of Example 1 is replaced by coal gangue. From the test results, it can be seen that when the system does not contain magnesium slag and carbide slag, the expansion ratio, compressive strength and carbon fixation rate of the material are greatly reduced. Since there is no magnesium slag and carbide slag in the system, the material cannot effectively chemically fix CO2, so that the material in the system cannot generate enough cementitious material, which further reduces the performance of the material. It can also be seen from Comparative Example 2 that although there is no magnesium slag and carbide slag in the system, the material still has a certain degree of expansion ratio, compressive strength and carbon fixation rate. This is because the presence of high water absorption resin monomer system and foaming agent and foam stabilizer makes a part of the pores solidify and remain, so that the material has a certain expansion ratio, compressive strength and carbon fixation rate. However, due to the lack of carbonates produced by the carbonization of magnesium slag and carbide slag in the system and the filling of gel materials, the strength of the grouting material is still greatly reduced compared with Example 1. It can be seen from Comparative Examples 1 and 2 that the CO2 content and the content of magnesium slag and carbide slag have a great influence on the performance of the material.

[0117] The comparative example 3 is a common industrial solid waste-based cementing grouting material on the market, and it can be found that the setting time of the comparative example 3 is 286 min, and the setting time of the examples 1-4 is between 17 min and 52 min, which shows that the acrylamide system greatly promotes the setting time of the material after being added. The technical system of the comparative example 3 is to form an alkaline environment in water by using alkaline solid waste such as red mud and carbide slag, to excite and activate materials such as desulfurization gypsum and mineral powder to generate tobermorite, and finally to solidify to form strength. There is an essential difference between the technology provided by the present application and the technology of the comparative example 3. The present application uses CO2 in industrial waste gas to wet carbonize the anhydrous hydration active magnesium slag, and then generates calcium carbonate and silica gel, so that the magnesium slag reaction product has cementing activity. Further, the carbide slag is added, which on the one hand forms a calcium hydroxide solution with water and generates C-S-H gel with the silica gel in the system to increase the density of the system and improve the material performance; on the other hand, the carbide slag reacts with water to release a large amount of heat, which causes the temperature of the system to rise, and then promotes the polymerization and cross-linking reaction of the acrylamide monomer in the system, so that the setting time of the material is shortened, the bubbles are solidified, and the polyacrylamide gel generated by the polymerization reaction of acrylamide is distributed on the bubble wall, so that the bubbles have a certain toughness and are more difficult to break. As can be seen from the proportioning of the two, the technology provided by the present application can solidify and cement more coal gangue fillers, because a large amount of acrylamide gel, silica gel and C-S-H gel are generated in the technical approach of the present application, so that more coal gangue fillers can be cemented, while the technology provided by the comparative example 3 generates a large amount of tobermorite which does not have cementing activity, so that a large amount of coal gangue fillers cannot be solidified. As can be seen, the technical ideas of the two are completely different, and the purpose of the carbide slag is also different. Since the alkaline environment in the technology of the comparative example 3 is very critical to the success of the system, it cannot introduce CO2 to excite the activity of the solid waste, and it also cannot achieve the technical approach of geological sequestration of CO2.

[0118] By Figure 1 It can be seen that after the carbonation and activation of the magnesium slag, the peak of dicalcium silicate gradually disappears, and the peak of calcium carbonate gradually increases, which shows that dicalcium silicate reacts with carbon dioxide to generate calcium carbonate, so that dicalcium silicate is consumed.

[0119] By Figure 2 It can be seen that the Si-O-Si vibration peak appears in the high-porosity gangue-based carbon sequestration filling grouting material obtained in the example 1, and the C-O vibration peak is strengthened, which shows that not only calcium carbonate is generated in the carbonation reaction process, but also amorphous silica gel is generated, that is, the following reaction occurs: C2S+2CO2→2CaCO3+SiO2(gel).

[0120] By Figure 3It can be seen that, under the addition of acrylamide system, foaming agent and foam stabilizer, the material forms a homogeneous high-pore structure.

[0121] By Figure 4 It can be seen that, under the joint action of various raw materials, a large amount of CaCO3 and C-S-H gel is generated in the grouting stone body, which is the reaction of amorphous silicon dioxide gel in the system and calcium hydroxide generated by the hydrolysis of carbide slag to produce C-S-H gel, that is, the following reaction occurs: SiO2(gel)+Ca(OH)2+H2O→C-S-H(gel).

[0122] Based on the above results, it can be seen that the introduction of industrial waste gas activates the magnesium slag by CO2 in the industrial waste gas, so that a large amount of CaCO3 and SiO2(gel) is generated, and the activity of the magnesium slag is excited. On the other hand, the material can form a homogeneous high-pore structure, and the presence of acrylamide system, foaming agent and foam stabilizer makes the pore structure uniform and not easy to break. The SiO2(gel), polyacrylamide gel and C-S-H(gel) in the system cement the coal gangue filler to form a high-pore carbon sequestration filling material, which can be used not only for filling mining grouting material, but also for CO2 geological sequestration.

[0123] From the above examples and comparative examples, it can be seen that the high-pore gangue-based carbon sequestration filling grouting material, the preparation method and the application provided by the present application have excellent solid waste treatment and CO2 sequestration and storage capacity. Due to the appropriate introduction of organic components in the system, the setting time of the material can be adjusted, and the expansion ratio can be controlled, which ensures the performance of the material, so that it meets the performance requirements of "high-pore", "fast setting", and "high carbon sequestration", so as to meet the use requirements of filling mining material.

[0124] The preferred embodiments of the present application are described in detail above in combination with the drawings, but the present application is not limited to the specific details in the above embodiments. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, and these simple modifications all belong to the protection scope of the present application.

[0125] In addition, various different embodiments of the present application can also be combined arbitrarily, as long as they do not deviate from the idea of the present application, and they should also be considered as disclosed by the present application.

Claims

1. A high porosity gangue-based carbon sequestration filling grouting material, characterized in that, The raw material components include, in parts by weight, 50-80 parts of coal gangue micro powder, 10-30 parts of magnesium slag micro powder, 5-20 parts of superabsorbent resin monomer, 0-5 parts of carbide slag micro powder, 0.05-0.3 parts of crosslinking agent, 0.1-0.5 parts of initiator, 0.1-0.6 parts of foaming agent, 0.1-0.3 parts of foam stabilizer, 60-100 parts of water, and 2-10 parts of CO2; The superabsorbent resin monomer includes acrylamide monomer; The crosslinking agent includes N,N-methylene bisacrylamide; The initiator includes industrial-grade ammonium persulfate and potassium persulfate; The foaming agent includes sodium dodecyl sulfate, protein foaming agent, cocoyl propyl betaine, and sodium alkenyl sulfonate.

2. The high porosity gangue-based carbon capture and sequestration grout material of claim 1, wherein, The coal gangue micro powder has a particle size of less than 100 mesh, the magnesium slag micro powder has a particle size of less than 200 mesh, and the carbide slag micro powder has a particle size of less than 200 mesh.

3. The high porosity gangue-based carbon capture and sequestration grout material of claim 1, wherein, The foam stabilizer is compounded from 30-40% calcium stearate and 60-70% sodium dodecyl benzene sulfonate surfactant.

4. A preparation method of a high-porosity gangue-based carbon sequestration filling and grouting material, characterized in that, The method includes the following steps: Step 1: mix the coal gangue micro powder with a particle size of less than 100 mesh and the magnesium slag micro powder with a particle size of less than 200 mesh at a speed of 50-100 r / min for 3-5 min to obtain mixed material A; mix the mixed material A with water at a speed of 100-200 r / min for 3-5 min to obtain slurry B; Step 2: add the formula amount of superabsorbent resin monomer, crosslinking agent, and initiator into the slurry B in sequence, and mix and stir at a speed of 100-200 r / min for 3-5 min to obtain slurry C; Step 3: add the formula amount of foaming agent and foam stabilizer into the slurry C, mix and stir at a speed of 200-300 r / min for 10-30 min, and continuously introduce industrial waste gas containing 10-20% CO2 during the stirring process at a rate of 1-3 mL / min / g to obtain slurry D; Step 4: add the carbide slag micro powder with a particle size of less than 200 mesh into the slurry D, and mix and stir at a speed of 100-200 r / min for 1-3 min to obtain the product. The coal gangue micro powder is 50-80 parts, the magnesium slag micro powder is 10-30 parts, the superabsorbent resin monomer is 5-20 parts, the carbide slag micro powder is 0-5 parts, the crosslinking agent is 0.05-0.3 parts, the initiator is 0.1-0.5 parts, the foaming agent is 0.1-0.6 parts, the foam stabilizer is 0.1-0.3 parts, the water is 60-100 parts, and the CO2 is 2-10 parts.

5. The production method according to claim 4, wherein The method includes the following steps: Step 1: mix the coal gangue micro powder with a particle size of less than 100 mesh and the magnesium slag micro powder with a particle size of less than 200 mesh at a speed of 50 r / min for 3 min to obtain mixed material A; mix the mixed material A with water at a speed of 100 r / min for 5 min to obtain slurry B; Step 2: add the formula amount of superabsorbent resin monomer, crosslinking agent, and initiator into the slurry B in sequence, and mix and stir at a speed of 200 r / min for 3 min to obtain slurry C; Step 3: add the formula amount of foaming agent and foam stabilizer into the slurry C, mix and stir at a speed of 200 r / min for 3 min to obtain slurry D; Step 3, adding the formula amount of foaming agent and foam stabilizer to the slurry C, mixing and stirring at a speed of 300 r / min for 20 min, and continuously introducing industrial waste gas with a carbon dioxide content of 10-20% at a rate of 3 mL / min / g during the stirring process to obtain slurry D; Step 4, adding the carbide slag powder with a particle size less than 200 mesh to the slurry D, mixing and stirring at a speed of 200 r / min for 2 min to obtain the slurry E; The coal gangue powder, the magnesium slag powder, the superabsorbent resin monomer, the carbide slag powder, the crosslinking agent, the initiator, the foaming agent, the foam stabilizer, the water and the CO2 are in a weight ratio of 50:30:20:5:0.2:0.4:0.3:0.1:90:

6.

6. Use of the high-porosity gangue-based carbon sequestration filling grouting material according to any one of claims 1-3 for filling mining.

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