K-type phosphate cement-based anchoring agent and preparation method thereof
By using cementitious materials with magnesium oxide, ferric oxide, and ferrous oxide as the main components, combined with phosphate curing agents and early-strength agents, a K-type phosphate cement-based anchoring agent was prepared. This solved the problems of poor adhesion of cement-based anchoring agents and safety risks of resin-based anchoring agents, and achieved high-performance anchoring effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-26
- Publication Date
- 2026-03-31
AI Technical Summary
Existing cement-based anchors are low in cost and have good weather resistance, but they have poor adhesion and poor early performance. Resin-based anchors have high safety risks and poor resistance to environmental degradation, which limits their application.
K-type phosphate cement-based anchoring agent is prepared by using cementitious materials with magnesium oxide, ferric oxide and ferrous oxide as the main components, combined with phosphate curing agents and early strength agents, through specific ratios and processes, to improve early strength and weather resistance.
It achieves a safe, low-cost anchoring effect with high pull-out strength, good early performance, and good weather resistance, and is suitable for coal mines and other fields.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of anchoring agent preparation technology. Specifically, this invention relates to a K-type phosphate cement-based anchoring agent and its preparation method. Background Technology
[0002] Anchoring agents are high-performance chemical materials widely used in building engineering, tunnel construction, mine support, and geological reinforcement. They are mainly used to firmly bond metal components such as steel bars, anchor rods, and bolts to concrete, rock, or other substrates to form a stable load-bearing structure. Their core function is to generate high-strength adhesive force through chemical reaction or physical curing, effectively transferring and dispersing loads, and improving the seismic resistance, durability, and overall stability of the structure.
[0003] The technological development of anchoring agents began in the mid-20th century. Early anchoring materials primarily used cement mortar, but due to its long curing time, low bond strength, and poor environmental adaptability, it was gradually replaced by chemical anchoring agents. In the 1960s, with the industrial application of epoxy and polyester resins, chemical anchoring agents began to emerge, quickly becoming mainstream due to their advantages such as rapid curing and high-strength adhesion. Since the 21st century, the development of environmentally friendly anchoring agents (such as solvent-free, low-VOC formulations) and specialty anchoring agents (high-temperature resistant, corrosion-resistant) has further expanded their application scenarios.
[0004] Commonly used anchoring agents are divided into cement-based anchoring agents and resin-based anchoring agents. Cement-based anchoring agents use cement as the main cementing material, and by adding accelerators and expanding agents, they mitigate problems such as shrinkage and poor early strength, which is why they have not been able to replace resin-based anchoring agents for a long time. At the same time, cement-based materials have lower costs and better weather resistance compared to resin-based anchoring agents, which is why industry professionals have continued to research them for many years. Resin-based anchoring agents, represented by unsaturated polyester resin-based anchoring agents, are currently the most commonly used anchoring agents. These anchoring agents introduce styrene as a solvent and crosslinking agent during processing. Styrene is a poisonous substance and is flammable and explosive. Furthermore, the initiator of these anchoring agents is an organic peroxide, which is not only flammable and explosive but also a controlled substance, greatly limiting its further application in the anchoring industry.
[0005] In summary, cement-based anchoring agents possess advantages such as low cost, good weather resistance, poor adhesion, and poor early performance, making them a potential replacement for resin-based anchoring agents. Resin-based anchoring agents, on the other hand, pose certain safety risks due to the raw materials used, and exhibit poor resistance to environmental degradation, slow curing speed at low temperatures, and poor early performance. Therefore, developing a universally applicable cement-based anchoring agent is of practical significance. Summary of the Invention
[0006] The present invention aims to at least partially solve one of the technical problems in the related art.
[0007] Therefore, embodiments of the present invention propose a K-type phosphate cement-based anchoring agent, which combines the advantages of cement-based anchoring agents and resin-based anchoring agents, and has advantages such as safety, low cost, high pull-out strength, good early performance, and good weather resistance.
[0008] The embodiments of the present invention also propose a method for preparing a K-type phosphate cement-based anchoring agent.
[0009] The K-type phosphate cement-based anchoring agent of this invention comprises the following components: cementitious material, curing agent, early strength agent, filler and water; wherein the cementitious material is made by high-temperature firing of magnesium oxide, ferric oxide and ferrous oxide.
[0010] This invention, through modification of phosphate cement and the introduction of an early-strength agent and filler, develops a K-type anchoring agent suitable for use in coal mines. This anchoring agent combines the advantages of both cement-based and resin-based anchoring agents, namely: safety, low cost, high pull-out strength, good early performance, and good weather resistance.
[0011] In some embodiments, the fineness of the magnesium oxide, the ferric oxide, and the ferrous oxide is not less than 600 mesh; And / or, the amount of magnesium oxide accounts for 18% to 36% of the mass of the cementitious material, the amount of ferric oxide accounts for 50% to 62% of the mass of the cementitious material, and the amount of ferrous oxide accounts for 0.1% to 36% of the mass of the cementitious material.
[0012] In some embodiments, the cementitious material is prepared by a method comprising the following steps: a) Magnesium oxide, ferric oxide and ferrous oxide are mixed and then calcined to obtain calcined powder; b) After cooling the calcined powder, crush it and separate the 200-mesh and 600-mesh powders. Then, mix the 200-mesh and 600-mesh powders to obtain the cementitious material.
[0013] In some embodiments, in step a), the mixing time is ≥2h; the heating rate of the calcination treatment is 1~3℃ / min, the calcination temperature is 1200~1500℃, and the calcination time is 1~4h; And / or, in step b), during compound mixing, the mass ratio of the 200-mesh powder to the 600-mesh powder is 3:1 to 7:1; the compound mixing time is ≥30 min.
[0014] In some embodiments, the curing agent is a mixture of potassium dihydrogen phosphate, ammonium dihydrogen phosphate, and phosphoric acid; Optionally, the mass ratio of potassium dihydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid is (3~5):1:(0.07~0.38); Optionally, the fineness of the potassium dihydrogen phosphate, the ammonium dihydrogen phosphate, and the phosphoric acid is not less than 200 mesh; And / or, the amount of the curing agent is 20% to 30% of the mass of the cementitious material.
[0015] In some embodiments, the early strength agent includes at least one of potassium bisulfate, ammonium bisulfate, aluminum dihydrogen phosphate, potassium bisulfite, and ammonium bisulfite; And / or, the fineness of the early strength agent is not less than 200 mesh; And / or, the amount of the early strength agent is 0.8% to 1.5% of the mass of the cementitious material.
[0016] In some embodiments, the filler is quartz sand, wherein the purity of the quartz sand is not less than 98% and the carbonate content is not more than 0.1%. Optionally, the quartz sand comprises 40 wt% coarse sand, 40 wt% medium sand and 20 wt% fine sand; the coarse sand has a particle size of 1.0~2.0 mm, the medium sand has a particle size of 0.5~1.0 mm, and the fine sand has a particle size of 0.08~0.5 mm. And / or, the amount of the filler accounts for 10% to 40% of the mass of the cementitious material.
[0017] In some embodiments, the K-type phosphate cement-based anchoring agent has a gel time of 60s to 90s, a compressive strength of ≥55MPa at 1h, a compressive strength of >60MPa at 1d, and a tensile strength of >150KN at 2h.
[0018] The preparation method of the K-type phosphate cement-based anchoring agent according to an embodiment of the present invention includes the following steps: (1) Mix the cementitious material and the filler to obtain component A; (2) After the curing agent is dried to constant weight, it is crushed and sieved to obtain component B; (3) Mix the early strength agent with water until it is completely dissolved and there is no precipitate to obtain component C; (4) Mix component B and component C until the mixture is a uniform paste, and then mix the resulting mixture with component A to obtain the K-type phosphate cement-based anchoring agent.
[0019] In some embodiments, in step (1), the mixing method is dry mixing, the mixing rate is not less than 300 r / min, and the mixing time is not less than 2 h; And / or, in step (2), the drying temperature is 150~200℃, the drying time is not less than 2h; the crushing time is not less than 10min, and the mesh size of the cured agent after crushing is not less than 200 mesh; And / or, in step (3), the amount of water used accounts for 8% to 12% of the mass of the cementitious material.
[0020] The features and advantages described above for K-type phosphate cement-based anchoring agents also apply to the preparation method of K-type phosphate cement-based anchoring agents, and will not be repeated here. Detailed Implementation
[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention without creative effort are within the protection scope of the present invention.
[0022] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
[0023] In this invention, when a value is described as a range, it should be understood that such disclosure includes disclosure of all possible subranges within that range, as well as specific numerical values falling within that range, regardless of whether specific numerical values or specific subranges are explicitly specified.
[0024] In this invention, the terms “comprising” and “including” and their various variations mean that other elements or wholes may be included but are not specifically described.
[0025] In this invention, the term "and / or" is merely a description of the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can represent three situations: A exists alone, A and B exist simultaneously, and B exists alone.
[0026] The K-type phosphate cement-based anchoring agent of this invention comprises the following components: cementitious material, curing agent, early strength agent, filler and water; wherein the cementitious material is made by high-temperature firing of magnesium oxide, ferric oxide and ferrous oxide.
[0027] It should be noted that the effective content of magnesium oxide (based on the mass of MgO) in the above-mentioned cementitious materials is not less than 95%, and the calcium oxide content (based on CaO) is not higher than 3%, with a fineness of not less than 325 mesh; the effective content of ferric oxide (based on the mass of Fe2O3) is not less than 95%, with a fineness of not less than 325 mesh; and the effective content of ferrous oxide (based on the mass of FeO) is not less than 95%, with a fineness of not less than 325 mesh. By using magnesium oxide, ferric oxide, and ferrous oxide to prepare the cementitious materials, the introduction of ferric oxide helps to lower the melting temperature of magnesium oxide and form spinel with it; the introduction of ferrous oxide helps to introduce ferrous ions, which can then react with the curing agent to generate an intermediate phase that is easier to precipitate and cement, thereby ensuring the continuity of the reaction between magnesium, ferric oxide, and the curing agent, and ensuring a steady increase in the performance of the anchoring agent.
[0028] In some embodiments, the fineness of the magnesium oxide, the ferric oxide, and the ferrous oxide is not less than 600 mesh; And / or, the amount of magnesium oxide accounts for 18% to 36% of the mass of the cementitious material, the amount of ferric oxide accounts for 50% to 62% of the mass of the cementitious material, and the amount of ferrous oxide accounts for 0.1% to 36% of the mass of the cementitious material.
[0029] In some embodiments, the cementitious material is prepared by a method comprising the following steps: a) Magnesium oxide, ferric oxide and ferrous oxide are mixed and then calcined to obtain calcined powder; b) After cooling the calcined powder, crush it and separate the 200-mesh and 600-mesh powders. Then, mix the 200-mesh and 600-mesh powders to obtain the cementitious material.
[0030] This invention employs a compounding of 200-mesh and 600-mesh powders (i.e., cementing materials). The 200-mesh cementing material has lower activity and reacts later than the 600-mesh material, providing a material basis for the continuous improvement of the anchoring agent's performance, and also exhibits lower heat of reaction. Conversely, the 600-mesh cementing material reacts more rapidly with the curing agent, ensuring early performance and providing higher anchoring force, but also exhibits higher heat of reaction. Using only 200-mesh powder results in lower early performance of the resulting anchoring agent; using only 600-mesh powder generates a huge amount of heat, leading to cracking of the cured anchoring agent.
[0031] In some embodiments, in step a), the mixing time is ≥2h; the heating rate of the calcination treatment is 1~3℃ / min, the calcination temperature is 1200~1500℃, and the calcination time is 1~4h; And / or, in step b), during compound mixing, the mass ratio of the 200-mesh powder to the 600-mesh powder is 3:1 to 7:1; the compound mixing time is ≥30 min.
[0032] In some embodiments, the curing agent is a mixture of potassium dihydrogen phosphate, ammonium dihydrogen phosphate, and phosphoric acid. By mixing these three as a curing agent, potassium dihydrogen phosphate has low reactivity, resulting in a low-strength cured body, but without odor release; ammonium dihydrogen phosphate has high reactivity, resulting in a high-strength cured body, but with ammonia release. Therefore, combining potassium dihydrogen phosphate and ammonium dihydrogen phosphate can reduce ammonia release while ensuring the strength of the cured body. Phosphoric acid is introduced because it is liquid at room temperature, which can dissolve potassium dihydrogen phosphate and ammonium dihydrogen phosphate, lower the pH value of the environment, appropriately increase the working time, and react rapidly with the cementitious material to generate a large amount of water, thereby shortening the slurry formation time and keeping the hydration products in the intermediate products to control the fluidity of the slurry and provide a large number of seed crystals for the final hydration products, resulting in rapid strength growth in a short time, i.e., "it doesn't harden until it does, and once it hardens, it quickly gains strength."
[0033] Optionally, the mass ratio of potassium dihydrogen phosphate, ammonium dihydrogen phosphate, and phosphoric acid is (3~5):1:(0.07~0.38). The inventors have found through research that if too much phosphoric acid is added, the slurry will become too thin, increasing its fluidity and making it easy to flow out of the borehole during construction, affecting the anchoring effect. At the same time, it will also increase the residence time of the intermediate product, resulting in slow performance growth. However, if too little phosphoric acid is added, the slurry forming speed will be too slow, increasing the mixing time and affecting the construction efficiency. Therefore, it is appropriate to control the mass ratio of potassium dihydrogen phosphate, ammonium dihydrogen phosphate, and phosphoric acid within the range of (3~5):1:(0.07~0.38) in the embodiments of the present invention. Optionally, the fineness of the potassium dihydrogen phosphate, the ammonium dihydrogen phosphate, and the phosphoric acid is not less than 200 mesh; And / or, the amount of the curing agent is 20% to 30% of the mass of the cementitious material.
[0034] In some embodiments, the early strength agent includes at least one of potassium bisulfate, ammonium bisulfate, aluminum dihydrogen phosphate, potassium bisulfite, and ammonium bisulfite; And / or, the fineness of the early strength agent is not less than 200 mesh; And / or, the amount of the early strength agent is 0.8% to 1.5% of the mass of the cementitious material.
[0035] In some embodiments, the filler is quartz sand, wherein the purity of the quartz sand is not less than 98% and the carbonate content is not more than 0.1%. Optionally, the quartz sand comprises 40 wt% coarse sand, 40 wt% medium sand, and 20 wt% fine sand; the coarse sand has a particle size of 1.0~2.0 mm, the medium sand has a particle size of 0.5~1.0 mm, and the fine sand has a particle size of 0.08~0.5 mm. By blending coarse, medium, and fine sand of different particle sizes, a dense packing can be formed, minimizing defects in the solidified body and thus improving the performance of the solidified body.
[0036] And / or, the amount of the filler accounts for 10% to 40% of the mass of the cementitious material.
[0037] In some embodiments, the K-type phosphate cement-based anchoring agent has a gel time of 60s to 90s, a compressive strength of ≥55MPa at 1h, a compressive strength of >60MPa at 1d, and a tensile strength of >150KN at 2h.
[0038] The preparation method of the K-type phosphate cement-based anchoring agent according to an embodiment of the present invention includes the following steps: (1) Mix the cementitious material and the filler to obtain component A; (2) After the curing agent is dried to constant weight, it is crushed and sieved to obtain component B; (3) Mix the early strength agent with water until it is completely dissolved and there is no precipitate to obtain component C; (4) Mix component B and component C until the mixture is a uniform paste, and then mix the resulting mixture with component A to obtain the K-type phosphate cement-based anchoring agent.
[0039] In some embodiments, in step (1), the mixing method is dry mixing, the mixing rate is not less than 300 r / min, and the mixing time is not less than 2 h; And / or, in step (2), the drying temperature is 150~200℃, the drying time is not less than 2h; the crushing time is not less than 10min, and the mesh size of the crushed curing agent is not less than 200 mesh; by crushing the curing agent, the mixture formed by the crushed curing agent component and component C can inhibit the crystallization and agglomeration of component A, thereby allowing the obtained anchoring agent to maintain a paste state for a long time; And / or, in step (3), the amount of water used accounts for 8% to 12% of the mass of the cementitious material.
[0040] The following are non-limiting embodiments and comparative examples of the present invention. It should be noted that the schemes in the comparative examples are not prior art, but are only set up for comparison with the schemes in the embodiments, and are not intended to limit the present invention. Unless otherwise stated, all raw materials used in the embodiments and comparative examples are conventional commercially available products, or can be prepared by known methods.
[0041] Example 1 This embodiment provides a K-type phosphate cement-based anchoring agent, comprising the following components: 100 parts by weight of cementitious material, 25 parts by weight of curing agent, 1 part by weight of early strength agent, 25 parts by weight of filler and 10 parts by weight of water.
[0042] In this embodiment, the cementitious material is prepared by a method comprising the following steps: a) Mix 18 parts by mass of magnesium oxide, 62 parts by mass of ferric oxide and 20 parts by mass of ferrous oxide for 3 h and then add them to the furnace. The furnace is heated to 1500℃ at a heating rate of 2℃ / min and held at that temperature for 4 h for calcination treatment to obtain calcined powder. b) After cooling the calcined powder, crush it and separate the 200-mesh and 600-mesh powders. Then, mix the 200-mesh and 600-mesh powders at a mass ratio of 3:1 to obtain the cementitious material.
[0043] In this embodiment, the curing agent is a mixture of potassium dihydrogen phosphate (325 mesh), ammonium dihydrogen phosphate (200 mesh) and phosphoric acid (200 mesh), and the mass ratio of the two is 3:1:0.38.
[0044] In this embodiment, the early strength agent is 200-mesh potassium bisulfite.
[0045] In this embodiment, the filler is quartz sand (purity 98%, carbonate content 0%), and the quartz sand is a compound of 40wt% coarse sand (particle size 1.0~2.0mm), 40wt% medium sand (particle size 0.5~1.0mm), and 20wt% fine sand (particle size 0.08~0.5mm).
[0046] This embodiment also provides a method for preparing the above-mentioned K-type phosphate cement-based anchoring agent, including the following steps: (1) Dry mix the cementitious material and the filler at a stirring rate of 300 r / min for 3 h to obtain component A; (2) Place the curing agent in an oven at 180°C to dry. Turn it over every 30 minutes during the drying process until it reaches a constant weight. Then place it in a pulverizer and crush it for 10 minutes until the mesh size is not less than 200 mesh. Sieve it to obtain component B. (3) Mix the early strength agent with water until it is completely dissolved and there is no precipitate to obtain component C; (4) Mix component B and component C until the mixture is a uniform paste, then mix the resulting mixture with component A to obtain type K phosphate cement-based anchoring agent.
[0047] Example 2 This embodiment provides a K-type phosphate cement-based anchoring agent, comprising the following components: 100 parts by weight of cementitious material, 30 parts by weight of curing agent, 0.8 parts by weight of early strength agent, 30 parts by weight of filler, and 8 parts by weight of water.
[0048] In this embodiment, the cementitious material is prepared by a method comprising the following steps: a) Mix 36 parts by mass of magnesium oxide, 50 parts by mass of ferric oxide and 14 parts by mass of ferrous oxide for 3 hours and then add them to the furnace. The furnace is heated to 1250°C at a heating rate of 2°C / min and held at that temperature for 2 hours for calcination to obtain calcined powder. b) After cooling the calcined powder, crush it and separate the 200-mesh and 600-mesh powders. Then, mix the 200-mesh and 600-mesh powders at a mass ratio of 7:1 to obtain the cementitious material.
[0049] In this embodiment, the curing agent is a mixture of potassium dihydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid, with a mass ratio of 5:1:0.08 and a fineness of 200 mesh.
[0050] In this embodiment, the early strength agent is a mixture of aluminum dihydrogen phosphate and ammonium bisulfate, with a mass ratio of 2:1 and a fineness of 200 mesh.
[0051] In this embodiment, the filler is quartz sand (purity 98%, carbonate content 0%), and the quartz sand is a compound of 40wt% coarse sand (particle size 1.0~2.0mm), 40wt% medium sand (particle size 0.5~1.0mm), and 20wt% fine sand (particle size 0.08~0.5mm).
[0052] This embodiment also provides a method for preparing the above-mentioned K-type phosphate cement-based anchoring agent, including the following steps: (1) Dry mix the cementitious material and the filler at a stirring rate of 300 r / min for 2 h to obtain component A; (2) Place the curing agent in an oven at 200°C to dry. Turn it over every 30 minutes during the drying process and dry it to constant weight. Then put it into a pulverizer and crush it for 10 minutes to make its mesh size not less than 200 mesh. Sieve it to obtain component B. (3) Mix the early strength agent with water until it is completely dissolved and there is no precipitate to obtain component C; (4) Mix component B and component C until the mixture is a uniform paste, then mix the resulting mixture with component A to obtain type K phosphate cement-based anchoring agent.
[0053] Example 3 This embodiment provides a K-type phosphate cement-based anchoring agent, comprising the following components: 100 parts by weight of cementitious material, 20 parts by weight of curing agent, 1.5 parts by weight of early strength agent, 40 parts by weight of filler, and 8 parts by weight of water.
[0054] In this embodiment, the cementitious material is prepared by a method comprising the following steps: a) Mix 20 parts by mass of magnesium oxide, 55 parts by mass of ferric oxide and 25 parts by mass of ferrous oxide for 3 hours and then add them to the furnace. The furnace is heated to 1500℃ at a heating rate of 3℃ / min and held at that temperature for 2 hours to obtain calcined powder. b) After cooling the calcined powder, crush it and separate the 200-mesh and 600-mesh powders. Then, mix the 200-mesh and 600-mesh powders at a mass ratio of 5:1 to obtain the cementitious material.
[0055] In this embodiment, the curing agent is a mixture of potassium dihydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid, with a mass ratio of 4:1:0.2 and a fineness of 200 mesh.
[0056] In this embodiment, the early strength agent is a mixture of aluminum dihydrogen phosphate, ammonium bisulfate, and potassium bisulfite, with a mass ratio of 2:1:1 and a fineness of 200 mesh.
[0057] In this embodiment, the filler is quartz sand (purity 98%, carbonate content 0%), and the quartz sand is a compound of 40wt% coarse sand (particle size 1.0~2.0mm), 40wt% medium sand (particle size 0.5~1.0mm), and 20wt% fine sand (particle size 0.08~0.5mm).
[0058] This embodiment also provides a method for preparing the above-mentioned K-type phosphate cement-based anchoring agent, including the following steps: (1) Dry mix the cementitious material and the filler at a stirring rate of 300 r / min for 2 h to obtain component A; (2) Place the curing agent in an oven at 150°C to dry. Turn it over every 30 minutes during the drying process until it reaches a constant weight. Then place it in a pulverizer and crush it for 10 minutes until the mesh size is not less than 200 mesh. Sieve it to obtain component B. (3) Mix the early strength agent with water until it is completely dissolved and there is no precipitate to obtain component C; (4) Mix component B and component C until the mixture is a uniform paste, then mix the resulting mixture with component A to obtain type K phosphate cement-based anchoring agent.
[0059] Example 4 This embodiment provides a K-type phosphate cement-based anchoring agent, comprising the following components: 100 parts by weight of cementitious material, 25 parts by weight of curing agent, 1.2 parts by weight of early strength agent, 40 parts by weight of filler and 12 parts by weight of water.
[0060] In this embodiment, the cementitious material is prepared by a method comprising the following steps: a) Mix 30 parts by mass of magnesium oxide, 50 parts by mass of ferric oxide and 20 parts by mass of ferrous oxide for 2 hours and then add them to the furnace. The furnace is heated to 1450°C at a heating rate of 3°C / min and held at that temperature for 4 hours to obtain calcined powder. b) After cooling the calcined powder, crush it and separate the 200-mesh and 600-mesh powders. Then, mix the 200-mesh and 600-mesh powders at a mass ratio of 4:1 to obtain the cementitious material.
[0061] In this embodiment, the curing agent is a mixture of potassium dihydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid, with a mass ratio of 3.5:1:0.38 and a fineness of 200 mesh.
[0062] In this embodiment, the early strength agent is a mixture of ammonium bisulfate and ammonium bisulfite, with a mass ratio of 1:2 and a fineness of 200 mesh.
[0063] In this embodiment, the filler is quartz sand (purity 98%, carbonate content 0%), and the quartz sand is a compound of 40wt% coarse sand (particle size 1.0~2.0mm), 40wt% medium sand (particle size 0.5~1.0mm), and 20wt% fine sand (particle size 0.08~0.5mm).
[0064] This embodiment also provides a method for preparing the above-mentioned K-type phosphate cement-based anchoring agent, including the following steps: (1) Dry mix the cementitious material and the filler at a stirring rate of 300 r / min for 2 h to obtain component A; (2) Place the curing agent in an oven at 200°C to dry. Turn it over every 30 minutes during the drying process and dry it to constant weight. Then put it into a pulverizer and crush it for 15 minutes to make its mesh size not less than 200 mesh. Sieve it to obtain component B. (3) Mix the early strength agent with water until it is completely dissolved and there is no precipitate to obtain component C; (4) Mix component B and component C until the mixture is a uniform paste, then mix the resulting mixture with component A to obtain type K phosphate cement-based anchoring agent.
[0065] The performance of the K-type phosphate cement-based anchoring agent prepared in the above embodiments and the commercially available unsaturated polyester anchoring agent were tested, and the results are shown in Table 1: Table 1
[0066] As can be seen from Table 1, the K-type phosphate cement-based anchoring agent prepared in the embodiments of the present invention has better mechanical properties than commercially available unsaturated polyester anchoring agents.
[0067] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.
[0068] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.
Claims
1. A type K phosphate cement-based anchoring agent, characterized in that, It comprises the following components: cementitious material, curing agent, early strength agent, filler and water; wherein the cementitious material is made by high-temperature firing of magnesium oxide, ferric oxide and ferrous oxide.
2. The K-type phosphate cement-based anchoring agent according to claim 1, characterized in that, The fineness of the magnesium oxide, the ferric oxide, and the ferrous oxide is not less than 600 mesh; And / or, the amount of magnesium oxide accounts for 18% to 36% of the mass of the cementitious material, the amount of ferric oxide accounts for 50% to 62% of the mass of the cementitious material, and the amount of ferrous oxide accounts for 0.1% to 36% of the mass of the cementitious material.
3. The K-type phosphate cement-based anchoring agent according to claim 1, characterized in that, The cementitious material is prepared by a method comprising the following steps: a) Magnesium oxide, ferric oxide and ferrous oxide are mixed and then calcined to obtain calcined powder; b) After cooling the calcined powder, crush it and separate the 200-mesh and 600-mesh powders. Then, mix the 200-mesh and 600-mesh powders to obtain the cementitious material.
4. The K-type phosphate cement-based anchoring agent according to claim 3, characterized in that, In step a), the mixing time is ≥2h; the heating rate of the calcination treatment is 1~3℃ / min, the calcination temperature is 1200~1500℃, and the calcination time is 1~4h. And / or, in step b), during compound mixing, the mass ratio of the 200-mesh powder to the 600-mesh powder is 3:1 to 7:1; the compound mixing time is ≥30 min.
5. The K-type phosphate cement-based anchoring agent according to claim 1, characterized in that, The curing agent is a mixture of potassium dihydrogen phosphate, ammonium dihydrogen phosphate, and phosphoric acid; Optionally, the mass ratio of potassium dihydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid is (3~5):1:(0.07~0.38); Optionally, the fineness of the potassium dihydrogen phosphate, the ammonium dihydrogen phosphate, and the phosphoric acid is not less than 200 mesh; And / or, the amount of the curing agent is 20% to 30% of the mass of the cementitious material.
6. The K-type phosphate cement-based anchoring agent according to claim 1, characterized in that, The early strength agent includes at least one of potassium bisulfate, ammonium bisulfate, aluminum dihydrogen phosphate, potassium bisulfite, and ammonium bisulfite. And / or, the fineness of the early strength agent is not less than 200 mesh; And / or, the amount of the early strength agent is 0.8% to 1.5% of the mass of the cementitious material.
7. The K-type phosphate cement-based anchoring agent according to claim 1, characterized in that, The filler is quartz sand, and the purity of the quartz sand is not less than 98% and the carbonate content is not more than 0.1%. Optionally, the quartz sand comprises 40 wt% coarse sand, 40 wt% medium sand and 20 wt% fine sand; the coarse sand has a particle size of 1.0~2.0 mm, the medium sand has a particle size of 0.5~1.0 mm, and the fine sand has a particle size of 0.08~0.5 mm. And / or, the amount of the filler accounts for 10% to 40% of the mass of the cementitious material.
8. The K-type phosphate cement-based anchoring agent according to any one of claims 1-7, characterized in that, The K-type phosphate cement-based anchoring agent has a gel time of 60s~90s, a compressive strength of ≥55MPa at 1h, a compressive strength of >60MPa at 1d, and a tensile strength of >150KN at 2h.
9. A method for preparing the K-type phosphate cement-based anchoring agent as described in any one of claims 1-8, characterized in that, Includes the following steps: (1) Mix the cementitious material and the filler to obtain component A; (2) After the curing agent is dried to constant weight, it is crushed and sieved to obtain component B; (3) Mix the early strength agent with water until it is completely dissolved and there is no precipitate to obtain component C; (4) Mix component B and component C until the mixture is a uniform paste, and then mix the resulting mixture with component A to obtain the K-type phosphate cement-based anchoring agent.
10. The method for preparing the K-type phosphate cement-based anchoring agent according to claim 9, characterized in that, In step (1), the mixing method is dry mixing, the mixing rate is not less than 300 r / min, and the mixing time is not less than 2 h; And / or, in step (2), the drying temperature is 150~200℃, the drying time is not less than 2h; the crushing time is not less than 10min, and the mesh size of the cured agent after crushing is not less than 200 mesh; And / or, in step (3), the amount of water used accounts for 8% to 12% of the mass of the cementitious material.