Organic-inorganic hybrid coal mine underground grouting plugging material and preparation method thereof

Abstract

The invention belongs to the technical field of geological mining, and particularly relates to an organic-inorganic hybrid coal mine underground grouting plugging material and a preparation method thereof. The grouting plugging material is synthesized by adopting an organic-inorganic hybridization mode, and comprises the following raw materials: sulphoaluminate cement, dimethylolpropionic acid, polyether polyol, aromatic isocyanate, a surfactant, polyether amine and the like. The grouting plugging material has the characteristics of good plugging effect of an inorganic grouting plugging material and rapid plugging of an organic grouting material, has the characteristics of low heat release, high expansion rate, good anti-corrosion effect and the like, and is suitable for plugging of various underground grouting plugging areas.

Description

Technical Field

[0001] The invention belongs to the technical field of organic-inorganic hybrid underground coal mine grouting and plugging materials, and particularly relates to an organic-inorganic hybrid underground coal mine grouting and plugging material and a preparation method thereof. Background Art

[0002] The roof of coal mine tunnels is generally composed of anisotropic rock mass, which is a complex medium formed by the cementation of various mineral components under geological action. There are natural defects such as cleavage, cracks, and intergranular pores in the rock mass. The rock mass has been weakened by groundwater for a long time, resulting in dripping and leakage, which reduces the strength of the surrounding rock in the mine and causes serious deformation. Even after taking reinforcement measures, the deformation is delayed, but during the mining period, the deformation of the water-sprinkling tunnel is aggravated, resulting in the roof plate sinking violently, and serious deformation of the two sides, which are hidden safety hazards. After the steel shed support is adopted, although the deformation of the tunnel is suppressed, the production efficiency of the tunnel is greatly affected, and safety hazards are buried. In addition, the support materials are severely corroded under the condition of long-term water immersion underground, which poses a threat to safe production. In order to avoid the instability of the tunnel, the research on grouting plugging materials and control technology in the water-sprinkling area is imminent.

[0003] At present, there are two main types of grouting and plugging in coal mines. One type mainly uses inorganic materials such as cement and water glass for grouting and plugging. This type of inorganic material has the characteristics of non-toxicity, slow heat release, and good plugging effect, but the grouting and plugging effect on large areas is not good, and the amount used is huge. The other type is organic foaming polymer materials. This type of grouting and plugging material has a good effect on foaming and plugging in large areas, and has obvious effects on the plugging and anti-corrosion of support water. However, due to the obvious heat release during the foaming reaction of organic foaming polymers, it has an adverse effect on underground safe construction, and its application in coal mines during most mining cycles is limited.

[0004] In view of the above-mentioned deficiencies of underground grouting and plugging materials in coal mines, how to combine the advantages of the two types of grouting and plugging materials to achieve plugging operations in various grouting areas in underground coal mines has become a key issue that needs to be urgently solved in the industry.

[0005] The present invention provides an organic-inorganic hybrid coal mine underground grouting plugging material and a preparation method thereof. The grouting plugging material is synthesized by an organic-inorganic hybrid method, has both the good plugging effect of inorganic grouting plugging materials and the rapid plugging characteristics of organic grouting materials, and has the characteristics of low heat release, high expansion ratio, good anti-corrosion effect, etc., and is suitable for plugging various grouting plugging areas underground. Summary of the invention

[0006] In order to overcome the above technical problems, the present invention provides an organic-inorganic hybrid coal mine underground grouting plugging material, which is synthesized by an organic-inorganic hybrid method, and has both the good plugging effect of inorganic grouting plugging materials and the rapid plugging characteristics of organic grouting materials, and has the characteristics of low heat release, high expansion ratio, good anti-corrosion effect, etc., and is suitable for plugging various grouting plugging areas underground.

[0007] To achieve the above objectives, the technical solution provided by the present invention is as follows: An organic-inorganic hybrid coal mine underground grouting plugging material comprises the following raw materials: sulphoaluminate cement, dimethylol propionic acid, polyether polyol, aromatic isocyanate, surfactant and polyether amine.

[0008] Preferably, the organic-inorganic hybrid coal mine underground grouting plugging material comprises the following raw materials in parts by weight: 10-50 parts of sulphoaluminate cement, 1-10 parts of dihydroxymethylpropionic acid, 10-50 parts of polyether polyol, 5-20 parts of aromatic isocyanate, 0.1-1 parts of surfactant, and 5-20 parts of polyether amine.

[0009] More preferably, the organic-inorganic hybrid coal mine underground grouting plugging material comprises the following raw materials, measured in parts by weight: 15-30 parts of sulphoaluminate cement, 2-5 parts of dihydroxymethylpropionic acid, 15-30 parts of polyether polyol, 10-15 parts of aromatic isocyanate, 0.2-0.8 parts of surfactant, and 8-15 parts of polyether amine.

[0010] Further, the polyether polyol is selected from any one or more of polyoxypropylene glycol, polytetrahydrofuran diol, tetrahydrofuran-oxypropylene copolymer glycol. Preferably, the molecular weight of the polyether polyol is 300-2000.

[0011] Preferably, the polyether polyol is selected from a mixture of polyoxypropylene glycol and polytetramethylene glycol; Furthermore, the aromatic isocyanate is selected from any one or more of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and naphthalene 1,5-diisocyanate (NDI).

[0012] Furthermore, the surfactant is selected from any one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, and fatty amine polyoxyethylene ether.

[0013] Furthermore, the fatty alcohol polyoxyethylene ether is selected from any one or more of polyethylene glycol ether, polyoctanol ether, lauryl alcohol polyoxyethylene ether, tetradecanol polyoxyethylene ether, hexadecanol polyoxyethylene ether, and octadecyl alcohol polyoxyethylene ether; preferably, any one or more of AEO-3, AEO-4, and AEO-5.

[0014] Furthermore, the alkylphenol polyoxyethylene ether is selected from at least one of octylphenol polyoxyethylene ether (OP) and nonylphenol polyoxyethylene ether (NP); preferably any one or more of OP-10, NP-4, NP-10, NP-30, and NP-50.

[0015] Furthermore, the fatty amine polyoxyethylene ether is selected from any one or more of tallow amine polyoxyethylene ether and dodecylamine polyoxyethylene ether.

[0016] Preferably, the surfactant is selected from any one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether or a combination thereof.

[0017] Furthermore, the polyetheramine is selected from any one or both of polyethylene glycol amine and polypropylene glycol amine.

[0018] Preferably, the molecular weight of the polyetheramine is 300-1000.

[0019] The present invention also aims to provide a method for preparing the organic-inorganic hybrid coal mine underground grouting plugging material, comprising the following steps: (1) Add polyether polyol into a reaction kettle, vacuum dehydrate, add aromatic isocyanate to react, then add dimethylol propionic acid to carry out chain extension reaction, gradually add sulphoaluminate cement, continue stirring and disperse into a paste; prepare grouting component A; (2) adding a surfactant to deionized water, dispersing the surfactant, and then slowly adding the polyetheramine to disperse the polyetheramine into an emulsion to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in proportion at the front end of the grouting pressure pump and then injected into the plugging position. After the injection is completed, solidification and plugging are achieved.

[0020] Preferably, the vacuum dehydration in (1) is carried out at 100-200° C. for 1-6 h.

[0021] Preferably, the reaction of adding aromatic isocyanate in (1) is carried out at 60-90° C. for 1-3 hours.

[0022] Preferably, the chain extension reaction time in (1) is 30-120 min.

[0023] Preferably, the sulphoaluminate cement in (1) has a mesh size of 100-200.

[0024] Preferably, the molecular weight of the polyetheramine in (2) is 300-1000.

[0025] Preferably, the method for preparing the organic-inorganic hybrid coal mine underground grouting plugging material comprises the following steps: (1) Add polyether polyol with a molecular weight of 300-2000 into a reaction kettle, perform vacuum dehydration at 100-120°C for 1-6 hours, add aromatic isocyanate and react at 60-90°C for 1 hour, add dimethylol propionic acid to carry out chain extension reaction, react for 30-120 minutes, gradually add 100-200 mesh sulphoaluminate cement, continue stirring and dispersing into a paste, and prepare grouting component A; (2) Adding a surfactant to deionized water, after dispersion, slowly adding a polyetheramine with a molecular weight of 300-1000, and dispersing it at high speed into an emulsion to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in a ratio of 1:1-5 at the front end of the grouting pressure pump and then injected into the plugging position. After the injection is completed, solidification and plugging are achieved.

[0026] The present invention also aims to provide the use of the organic-inorganic hybrid underground coal mine grouting plugging material in underground coal mine grouting plugging agents.

[0027] Compared with the prior art, the technical advantages of the present invention are: (1) The present invention provides an organic-inorganic hybrid coal mine underground grouting plugging material and a preparation method thereof. The grouting plugging material is synthesized by an organic-inorganic hybrid method, and has both the good plugging effect of inorganic grouting plugging materials and the rapid plugging characteristics of organic grouting materials, and has the characteristics of low heat release, high expansion ratio, good anti-corrosion effect, etc., and is suitable for plugging various grouting plugging areas underground.

[0028] (2) The organic-inorganic hybridization method adopted enables the inorganic sulfoaluminate plugging material to be compounded with the organic material, and the performance of the synthesized material is stable.

[0029] (3) The addition of inorganic components reduces the heat release rate of the organic foaming material during the reaction process, avoiding problems such as core burning and combustion caused by concentrated heat release, and improving the safety of underground construction. The foaming effect of organic components can make up for the problems of large amount of inorganic grouting and poor corrosion resistance, and the plugging effect is obvious for large areas and water sprinkling areas. DETAILED DESCRIPTION

[0030] The present invention is described below by specific examples to make the technical solution of the present invention easier to understand and grasp, but the present invention is not limited thereto. The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified. The molecular weights described in the present invention refer to the weight average molecular weight; the strength grade of sulphoaluminate cement is 42.5. Example

[0031] A method for preparing an organic-inorganic hybrid coal mine underground grouting plugging material comprises the following steps: (1) 8 parts of polyoxypropylene glycol with a molecular weight of 1000 and 10 parts of polytetrahydrofuran diol with a molecular weight of 800 are added to a reaction kettle, vacuum dehydrated at 120° C. for 2 hours, 14 parts of MDI are added, reacted at 80° C. for 1 hour, 2 parts of dimethylol propionic acid are added for chain extension reaction, and after reacting for 30 minutes, 20 parts of 100-200 mesh sulphoaluminate cement are gradually added, and stirring and dispersing is continued for 30 minutes to form a paste; thereby preparing grouting component A; (2) After adding 0.1 parts of AEO-3, 0.2 parts of NP-10, and 0.1 parts of dodecylamine polyoxyethylene ether to deionized water for dispersion, 10 parts of polypropylene glycol amine with a molecular weight of 1000 was slowly added and dispersed into an emulsion at a high speed to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in a mass ratio of 1:1 at the front end of the grouting pressure pump and injected into the plugging position. After the injection is completed, the solidification and plugging are achieved in 5-10 minutes. Example

[0032] A method for preparing an organic-inorganic hybrid coal mine underground grouting plugging material comprises the following steps: (1) 18 parts of polyoxypropylene glycol with a molecular weight of 1000 were added to a reactor, vacuum dehydrated at 120°C for 2 hours, 14 parts of TDI were added, reacted at 80°C for 1 hour, 2 parts of dimethylol propionic acid were added for chain extension reaction, and after reacting for 30 minutes, 20 parts of 100-200 mesh sulphoaluminate cement were gradually added, and stirring and dispersing continued for 30 minutes to form a paste; thus, grouting component A was prepared; (2) Add 0.4 parts of AEO-3 to deionized water, disperse it, and then slowly add 10 parts of polypropylene glycol amine with a molecular weight of 1000 and disperse it at high speed into an emulsion to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in a ratio of 1:2 at the front end of the grouting pressure pump and injected into the plugging position. After the injection is completed, the solidification and plugging are achieved in 5-10 minutes. Example

[0033] A method for preparing an organic-inorganic hybrid coal mine underground grouting plugging material comprises the following steps: (1) 8 parts of polyoxypropylene glycol with a molecular weight of 1000 and 12 parts of tetrafuran-propylene oxide copolymer glycol with a molecular weight of 800 are added to a reactor, vacuum dehydrated at 120° C. for 2 hours, 14 parts of NDI are added, reacted at 80° C. for 1 hour, 2 parts of dimethylol propionic acid are added for chain extension reaction, and after reacting for 30 minutes, 20 parts of 100-200 mesh sulphoaluminate cement are gradually added, and stirring and dispersing is continued for 30 minutes to form a paste; thus, grouting component A is prepared; (2) After adding 0.1 parts of AEO-5, 0.2 parts of OP-10 and 0.2 parts of NP-30 to deionized water and dispersing them, 10 parts of polypropylene glycol amine with a molecular weight of 1000 was slowly added and dispersed into an emulsion at a high speed to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in a ratio of 1:4 at the front end of the grouting pressure pump and injected into the plugging position. After the injection is completed, the solidification and plugging are achieved in 5-10 minutes. Example

[0034] A method for preparing an organic-inorganic hybrid coal mine underground grouting plugging material comprises the following steps: (1) 10 parts of polytetrahydrofuran diol with a molecular weight of 2000 are added to a reactor, vacuum dehydrated at 100° C. for 2 hours, 15 parts of NDI are added, reacted at 80° C. for 1 hour, 5 parts of dimethylol propionic acid are added for chain extension reaction, and after reacting for 120 minutes, 20 parts of 100-200 mesh sulphoaluminate cement are gradually added, and stirring and dispersing is continued for 30 minutes to form a paste; thus, grouting component A is prepared; (2) After adding 0.1 parts of AEO-5, 0.2 parts of OP-10 and 0.2 parts of NP-30 to deionized water and dispersing them, 10 parts of polypropylene glycol amine with a molecular weight of 300 was slowly added and dispersed into an emulsion at a high speed to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in a ratio of 1:3 at the front end of the grouting pressure pump and injected into the plugging position. After the injection is completed, the solidification and plugging are achieved in 5-10 minutes. Example

[0035] (1) Add 2 parts of polyoxypropylene glycol with a molecular weight of 1500 and 8 parts of tetrafuran-propylene oxide copolymer glycol with a molecular weight of 300 into a reactor, vacuum dehydrate at 120°C for 1 hour, add 5 parts of NDI, react at 60°C for 3 hours, add 1 part of dimethylol propionic acid for chain extension reaction, react for 120 minutes, gradually add 10 parts of 100-200 mesh sulphoaluminate cement, continue stirring and dispersing for 30 minutes to form a paste; prepare grouting component A; (2) After adding 0.1 parts of AEO-3 to deionized water for dispersion, 5 parts of polypropylene glycol amine with a molecular weight of 1000 was slowly added and dispersed into an emulsion at a high speed to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in a ratio of 1:5 at the front end of the grouting pressure pump and injected into the plugging position. After the injection is completed, the solidification and plugging are achieved in 5-10 minutes. Example

[0036] (1) Add 2 parts of polyoxypropylene glycol with a molecular weight of 1500 and 8 parts of polytetrahydrofuran diol with a molecular weight of 300 into a reactor, vacuum dehydrate at 100° C. for 6 hours, add 4 parts of NDI, react at 90° C. for 1 hour, add 2 parts of dimethylol propionic acid for chain extension reaction, react for 30 minutes, gradually add 10 parts of 100-200 mesh sulphoaluminate cement, continue stirring and dispersing for 30 minutes to form a paste, and prepare grouting component A; (2) After adding 0.1 parts of AEO-5 and 0.1 parts of OP-10 to deionized water and dispersing them, 4 parts of polypropylene glycol amine with a molecular weight of 1000 were slowly added and dispersed into an emulsion at a high speed to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in a ratio of 1:1 at the front end of the grouting pressure pump and injected into the plugging position. After the injection is completed, the solidification and plugging are achieved in 5-10 minutes.

[0037] (1) 8 parts of polyoxypropylene glycol with a molecular weight of 200 and 10 parts of polytetrahydrofuran diol with a molecular weight of 3000 are added to a reaction kettle, vacuum dehydrated at 120° C. for 2 hours, 14 parts of MDI are added, reacted at 80° C. for 1 hour, 2 parts of dimethylol propionic acid are added for chain extension reaction, and after reacting for 30 minutes, 20 parts of 100-200 mesh sulphoaluminate cement are gradually added, and stirring and dispersing is continued for 30 minutes to form a paste; thereby preparing grouting component A; (2) After adding 0.1 parts of AEO-5, 0.2 parts of NP-10, and 0.1 parts of dodecylamine polyoxyethylene ether to deionized water for dispersion, 10 parts of polypropylene glycol amine with a molecular weight of 1500 was slowly added and dispersed into an emulsion at a high speed to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in a ratio of 1:0.5 at the front end of the grouting pressure pump and then injected into the plugging position.

[0038] The inorganic grouting plugging material was prepared with reference to Example 1 described in the prior art CN105481324A.

[0039] An inorganic grouting plugging material, comprising the following raw materials in parts by weight: 75 parts of silicate cement clinker; 3 parts of slag; 5 parts of sulphoaluminate cement; 0.5 parts of bentonite; 0.05 parts of hydroxyethyl cellulose ether; 0.25 parts of water reducing agent; 0.005 parts of lithium carbonate; 0.05 parts of defoaming agent (the specific surface area of ​​the slag used is 623 kg / m 3 The bentonite is sodium bentonite with a water absorption rate of 600% to 650% and a 80 μm sieve residue of 7-8%; the viscosity of the hydroxyethyl cellulose ether is 25000 mPa·s; the water reducer is a polycarboxylic acid water reducer with a water reduction rate of 32.5%; and the defoamer is an emulsified silicone oil defoamer).

[0040] Comparative Example 3 Commercially available sulphoaluminate cement, strength grade 42.5.

[0041] Test method: According to the preparation method of an organic-inorganic hybrid coal mine underground grouting plugging material provided by the present invention, a synthetic embodiment is obtained, and the grouting ratio is cured in a mold with a length of 25 cm, a width of 2.5 cm, and a thickness of 0.5 cm. Samples are taken at 10 minutes, 30 minutes, 100 minutes, and 200 minutes, respectively, and the tensile strength and compressive strength of the grouting material are detected. In a cylindrical container with a bottom diameter of 5 cm, 10g of grouting material mixed according to the grouting ratio is added, and the vertical expansion rate of 3d is observed and measured. A square sample of 20cm×20cm×5cm is prepared, and the permeability coefficient is tested on an SS-25 concrete impermeability tester (the medium is water, the pressure of the impermeability tester is set to 2MPa, the water flow rate is 0.1L / min, and the test results at 90d age shall prevail). The above-mentioned test methods are all conventional technical means in this field, and will not be repeated here. Different embodiments and comparative examples are tested under the same conditions. The experimental results are shown in Table 1 below.

[0042] Table 1 Performance test results Note: a means that its mechanical strength cannot be measured because it is in liquid or semi-solid state.

[0043] From the above data, it can be seen that the organic-inorganic hybrid coal mine underground grouting plugging material provided by the present invention has high tensile strength and compressive strength, and also shows very excellent levels in terms of vertical expansion rate and permeability coefficient, and has a significant plugging effect.

[0044] The above detailed description is a specific description of one feasible embodiment of the present invention. The embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification that does not deviate from the present invention should be included in the scope of the technical solution of the present invention.

Claims

1. An organic-inorganic hybrid coal mine underground grouting plugging material: prepared from the following raw materials in parts by weight: 10-50 parts of sulphoaluminate cement, 1-10 parts of dimethylol propionic acid, 10-50 parts of polyether polyol, 5-20 parts of aromatic isocyanate, 0.1-1 parts of surfactant, and 5-20 parts of polyether amine; the molecular weight of the polyether polyol is 300-2000, and the molecular weight of the polyether amine is 300-1000.

2. The organic-inorganic hybrid coal mine underground grouting plugging material as described in claim 1 is prepared from the following raw materials in parts by weight: 15-30 parts of sulphoaluminate cement, 2-5 parts of dimethylol propionic acid, 15-30 parts of polyether polyol, 10-15 parts of aromatic isocyanate, 0.2-0.8 parts of surfactant, and 8-15 parts of polyether amine.

3. The organic-inorganic hybrid underground coal mine grouting plugging material according to claim 1, wherein the polyether polyol is selected from any one or more of polyoxypropylene glycol, polytetrahydrofuran diol, and tetrahydrofuran-oxypropylene copolymer glycol; More preferably, the polyether polyol is selected from a mixture of polyoxypropylene glycol and polytetramethylene glycol.

4. The organic-inorganic hybrid underground coal mine grouting plugging material according to claim 1, wherein the aromatic isocyanate is selected from any one or more of toluene diisocyanate, diphenylmethane diisocyanate, and naphthalene 1,5-diisocyanate.

5. The organic-inorganic hybrid underground coal mine grouting plugging material according to claim 1, wherein the surfactant is selected from any one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, and fatty amine polyoxyethylene ether; Preferably, the fatty alcohol polyoxyethylene ether is selected from any one or more of polyethylene glycol ether, polyoctanol ether, lauryl alcohol polyoxyethylene ether, tetradecanol polyoxyethylene ether, hexadecanol polyoxyethylene ether, and octadecyl alcohol polyoxyethylene ether; preferably, any one or more of AEO-3, AEO-4, and AEO-5; Preferably, the alkylphenol polyoxyethylene ether is selected from at least one of octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether; preferably any one or more of OP-10, NP-4, NP-10, NP-30, and NP-50; Preferably, the fatty amine polyoxyethylene ether is selected from any one or more of tallow amine polyoxyethylene ether and dodecylamine polyoxyethylene ether.

6. The organic-inorganic hybrid coal mine underground grouting plugging material according to claim 1, wherein the polyetheramine is selected from any one or both of polyethylene glycol amine and polypropylene glycol amine.

7. The organic-inorganic hybrid underground coal mine grouting plugging material according to claim 6, comprising a grouting component A and a grouting component B, wherein the raw materials for preparing the grouting component A are polyether polyol, aromatic isocyanate, dimethylol propionic acid, and sulphoaluminate cement; the raw materials for preparing the grouting component B are surfactants and polyetheramines; Preferably, the dosage ratio of the grouting component A to the grouting component B is 1:1-5.

8. The method for preparing the organic-inorganic hybrid coal mine underground grouting plugging material according to claim 1 comprises the following steps: (1) Add polyether polyol into a reaction kettle, vacuum dehydrate, add aromatic isocyanate to react, then add dimethylol propionic acid to carry out chain extension reaction, gradually add sulphoaluminate cement, continue stirring and disperse into a paste; prepare grouting component A; (2) adding a surfactant to deionized water, dispersing the surfactant, and then slowly adding the polyetheramine to disperse the polyetheramine into an emulsion to prepare a grouting component B; (3) The prepared grouting component A and grouting component B are mixed in proportion at the front end of the grouting pressure pump and then injected into the plugging position. After the injection is completed, solidification and plugging are achieved.

9. Application of the organic-inorganic hybrid coal mine underground grouting plugging material as claimed in claim 1 in coal mine underground grouting plugging agent.

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