CN115286305A - A kind of soil cave or karst cave filling grouting material and preparation method thereof - Google Patents

Abstract

The invention provides an earth cave or karst cave filling grouting material and a preparation method thereof, which are prepared from the following raw materials in parts by mass: 240-360 parts of cement, 80-100 parts of fly ash and 680-910 parts of tailing sand , 80-100 parts of expanded slag, 210-280 parts of coal gangue powder, 3-5 parts of modified nanofiber material, 50-120 parts of additives and 550-750 parts of water; the modified nano-fiber material is prepared by the following method Obtained: soak the pretreated waste wood raw materials in polyethylene glycol aqueous solution, add laccase, adjust the pH to 4-5 with buffer, and then activate the reaction at 35-40 ℃ for 1-2 hours; then transfer to water, Cooking to inactivate laccase; then adding cationic styrene-acrylic emulsion and ball milling to obtain modified nanofiber material. The invention solves the problem of re-collapse of soil caves or karst caves in the construction area and the problem that the existing filling grouting materials are easily pulverized after being broken.

Description

A soil cave or karst cave filling grouting material and preparation method thereof

technical field

The invention relates to the technical field of filling materials, in particular to a soil cave or karst cave filling grouting material and a preparation method thereof.

Background technique

During engineering construction in karst development areas, unfavorable geological effects such as soil caves and karst caves are often encountered, and it is necessary to carry out grouting reinforcement for soil caves or karst caves; the development of soil caves or karst caves is irregular, and the actual survey process often affects its scale. It is difficult to find out, which has a great impact on the project cost; and the conditions for the development of soil caves or karst caves generally have the characteristics of abundant groundwater and high mobility, which makes the amount of grouting in soil caves or karst caves more uncertain. Therefore, soil caves or karst caves The economy of grouting materials has become an important factor to control the project cost.

The amount of grouting in soil caves or karst caves in the karst area is extremely large. At the same time, the output of tailings sand (powder) in the mining area is large, and the part of the tailings waste sand is used for backfilling the goaf, and the efficiency of resource utilization is low. A large amount of waste powder from mine tailings accumulates, which not only causes a waste of resources, but also easily induces secondary disasters, posing a threat to resources, the environment, ecology and safety. The tailings waste sand (powder) is used as the grouting material, which can turn waste into treasure and respond to the government's green environmental protection requirements. The success of the new ratio is expected to greatly save the cost, and the market application has a positive effect. Therefore, in order to realize the resource utilization of mine solid waste, it is necessary to comprehensively treat the solid tailing waste combined with the filling requirements of goafs, soil caves, and karst caves. While reducing the hazards of mine solid waste, it can also be used as soil waste. Hole or cave filling materials for resource utilization, turning waste into treasure.

At present, copper ore tailings are used as the main raw material, mixed with partial dickite and alkali activator prepared by potassium acetate intercalation and calcined, and then cured to prepare filling materials suitable for underground soil caves or caves. Using Zijinshan copper mine tailings as raw materials, dickite prepared by intercalating and calcining dickite with potassium acetate as additive, water glass and sodium hydroxide as alkali activator, the filling material is prepared. It has rich sources of raw materials, high resource utilization rate, simple and efficient process flow, economical and practical, green and environmental protection, and has good industrial prospects and social benefits.

However, although the filling material prepared by this method can be used for filling underground cavities or karst caves, the strength of the filling material prepared from copper ore tailings is not high, and the problem of re-collapse of soil or karst caves is prone to occur, and after the collapse, the original The solidified body formed by the filling material is easily pulverized after being broken, which will aggravate the collapse of the soil cavity or cave.

Contents of the invention

In order to solve the above technical problems, the object of the present invention is to provide a soil cave or cave filling grouting material and a preparation method thereof.

To achieve the above object, the technical solution of the present invention is as follows.

A soil cave or karst cave filling grouting material is prepared from the following raw materials in parts by mass:

240-360 parts of cement, 80-100 parts of fly ash, 680-910 parts of tailings sand, 80-100 parts of expanded slag, 210-280 parts of coal gangue powder, 3-5 parts of modified nanofiber material, 50-120 parts of additives 550-750 parts of water and 550 parts;

The modified nanofibrous material is prepared by the following method:

Soak the pretreated waste wood material in aqueous polyethylene glycol solution, add laccase, adjust the pH to 4-5 with buffer solution, and then activate the reaction at 35-40°C for 1-2 hours; then transfer the activation solution into water , heat treatment at 110-130° C. for 10-15 s; then add cationic styrene-acrylic emulsion and ball mill to obtain modified nanofiber material.

In the present invention, in the preparation process of the modified nanofibrous material, firstly, laccase is used to activate the waste wood raw material, so that the macromolecular lignin in the wood material is broken and degraded to a certain extent, while increasing the surface hydroxyl content, Small amounts of ether linkages are also formed. At the same time, ammonia gas/air is introduced during the activation process, a small amount of ammonia gas reacts with the buffer solution to generate ammonium acetate or ammonium citrate, and the generated ammonium acetate or ammonium citrate is used to modify the nanocellulose, and heat treatment is used. While the laccase is inactivated, the breaking strength of the modified nanocellulose is further improved. Then, the lignonanocellulose is modified by cationic styrene-acrylic emulsion to improve the cohesiveness and dispersibility of the lignonanocellulose. Further, the additives include early strength agents, water reducing agents and alkali activators.

Furthermore, among the additives, the mass ratio of the early strength agent, the alkali activator, and the water reducer is 1:1:0.1-0.3.

Furthermore, the early strength agent is a mixture of sodium sulfite, calcium chloride and Glauber's salt in a mass ratio of 1:1:2-3;

The water reducer is a polycarboxylate water reducer;

The alkali activator is a mixture of sodium hydroxide and sodium silicate at a mass ratio of 1:1-2.

Further, the polyethylene glycol aqueous solution is formed by mixing polyethylene glycol and water at a volume ratio of 1:0.2-0.6;

The dosage ratio of waste woody raw materials and polyethylene glycol aqueous solution is 1g: 4-8mL.

Further, the dosage of laccase is 18-28 IU/g.

Further, the buffer is acetic acid-sodium acetate buffer, citric acid-sodium citrate buffer or citric acid-disodium hydrogen phosphate buffer;

The waste wood raw material is waste wood or waste straw; the waste straw is any one of corn straw, wheat straw and cotton straw;

The pretreatment process of the waste woody raw material is as follows: the waste woody raw material is pulverized and soaked in a buffer solution for 8-12 hours, filtered and dried to obtain the finished product.

Further, during the activation reaction process of the waste wood raw material, a mixed gas is introduced at a flow rate of 30mL/min. The mixed gas is formed by mixing ammonia and air, and the ammonia gas accounts for 5-10% by volume of the mixed gas.

Further, the mass ratio of the waste woody raw material to the cationic styrene-acrylic emulsion is 1:0.3-0.6.

The present invention also provides a method for preparing grouting material for filling soil caves or karst caves, comprising the following steps:

S1. Weigh each raw material according to the ratio;

S2. Add sodium hydroxide and sodium silicate to the tailing sand according to the mass ratio of 1:1~2, mix and vibrate and grind, and then place it at 350-450°C for calcination for 1-2 hours, and then vibrate the material to obtain Activated tailings sand;

S3, uniformly mixing the activated tailings sand with fly ash, expanded slag, and coal gangue powder to obtain a mixture;

S4. Mix the modified nanofibrous material with water evenly, add the mixture, early strength agent and water reducer, after mixing evenly, add cement, continue to mix and mix, and obtain the soil cave or cave filling grouting material.

Beneficial effects of the present invention:

1. The present invention utilizes tailings sand, expanded slag, fly ash, coal gangue powder and other wastes to compound with cement and other materials to prepare grouting materials for filling soil caves or karst caves, and to deal with unfavorable geology such as soil caves and karst caves. , to solve the problem of re-collapse of soil caves or karst caves and the problem that the existing filling grouting materials are easy to pulverize after being broken.

2. The present invention utilizes sodium hydroxide and sodium silicate to activate the iron tailings sand to improve the activity of the iron tailings sand; and the multi-component system formed by iron tailings sand, expanded slag and other slag content helps to improve the effect on soil The compressive strength of cave or cave filling grouting material.

3. The present invention utilizes laccase to activate the waste wood raw material, so that the macromolecular lignin in the wood material will be broken and degraded to a certain extent, and a small amount of ether bonds will be formed while increasing the surface hydroxyl content. A small amount of ammonia gas introduced during the activation process can react with acetic acid or citric acid in the buffer to generate ammonium acetate or ammonium citrate, and use the generated ammonium acetate or ammonium citrate to modify nanocellulose to further improve the performance of modified nanofibers. The breaking strength of cellulose. Then, the lignonanocellulose is modified by cationic styrene-acrylic emulsion to improve the cohesiveness and dispersibility of the lignonanocellulose. Mixing the modified nanofiber material with tailings sand and other wastes can improve the interface adhesion, as well as the overall strength and tensile properties, so as to solve the problem that the existing filling and grouting materials are easy to pulverize after being broken.

4. The grouting material for filling soil caves or karst caves of the present invention has a simple preparation process, low cost, economical and environmental protection, and is suitable for popularization and application.

Detailed ways

In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

Laccase, from Sigma.

The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials can be purchased in the market unless otherwise specified.

Example 1

A soil cave or karst cave filling grouting material is prepared from the following raw materials in parts by mass:

300 parts of cement, 90 parts of fly ash, 900 parts of tailings sand, 90 parts of expanded slag, 260 parts of coal gangue powder, 4.5 parts of modified nanofiber material, 100 parts of additives and 700 parts of water.

The additives include an early strength agent, a water reducer and a base activator, and the mass ratio of the early strength agent, the base activator and the water reducer is 1:1:0.2. The early strength agent is a mixture of sodium sulfite, calcium chloride, and Glauber's salt in a mass ratio of 1:1:2.3; the water reducer is a polycarboxylate water reducer; the alkali activator is sodium hydroxide and sodium silicate by mass The ratio is 1:1.5 for mixing.

A method for preparing a grouting material for filling a soil cave or a karst cave, comprising the following steps:

S1. Weigh each raw material according to the ratio;

S2, preparation of modified nanofiber material:

S2.1, cut the corn stalks into small pieces, soak them in a citric acid-sodium citrate buffer solution with a pH of 4.5 for 10 hours, the amount of the citric acid-sodium citrate buffer solution is to submerge the corn stalks, and then filter. The filter residue was rinsed with distilled water and dried in an oven at 45°C to obtain pretreated waste woody material.

S2.2. Mix polyethylene glycol and water in a volume ratio of 1:0.4 to obtain an aqueous solution of polyethylene glycol.

S2.3. Soak the pretreated waste woody material in polyethylene glycol aqueous solution, then add 25IU/g laccase, adjust the pH of the solution to 4.5 with citric acid-sodium citrate buffer solution, and activate the reaction at 40°C 1.5h; During the activation process, a mixed gas of ammonia/air was introduced at a flow rate of 30 mL/min, and the volume percentage of ammonia in the mixed gas was 8%.

S2.4. Transfer the activation solution of S2.3 into water according to the volume ratio of 1:75, and heat-treat at 125°C for 12s to inactivate laccase; then according to the mass ratio of waste wood raw materials and cationic styrene-acrylic emulsion to 1: 0.45 Add cationic styrene-acrylic emulsion and ball mill to obtain modified nanofiber material.

S3. Mix sodium hydroxide and sodium silicate according to the mass ratio of 1:1.5 as an alkali stimulator, add it to the tailings sand, mix and vibrate, then place it at 420°C for 1.5h, and then vibrate the material. Get activated tailings sand;

S4, uniformly mixing the activated tailings sand with fly ash, expanded slag, and coal gangue powder to obtain a mixture;

S5. Mix the modified nanofibrous material with water evenly, add the mixture, early strength agent and water reducing agent, after mixing evenly, add cement, continue to mix and mix, and obtain the grouting material for filling the soil cave or karst cave.

Example 2

A soil cave or karst cave filling grouting material is prepared from the following raw materials in parts by mass:

360 parts of cement, 100 parts of fly ash, 910 parts of tailings sand, 100 parts of expanded slag, 280 parts of coal gangue powder, 5 parts of modified nanofiber material, 120 parts of additives and 750 parts of water.

The additives include an early strength agent, a water reducer and a base activator, and the mass ratio of the early strength agent, the base activator and the water reducer is 1:1:0.3. The early strength agent is a mixture of sodium sulfite, calcium chloride, and Glauber's salt in a mass ratio of 1:1:3; the water reducer is a polycarboxylate water reducer; the alkali activator is sodium hydroxide and sodium silicate by mass The ratio is 1:2 for mixing.

A method for preparing a grouting material for filling a soil cave or a karst cave, comprising the following steps:

S1. Weigh each raw material according to the ratio;

S2, preparation of modified nanofiber material:

S2.1, cut the corn stalks into small pieces, soak them in a citric acid-sodium citrate buffer solution with a pH of 5 for 8 hours, the amount of the citric acid-sodium citrate buffer solution is to submerge the corn stalks, and then filter. The filter residue was rinsed with distilled water and dried in an oven at 50°C to obtain pretreated waste woody material.

S2.2. Mix polyethylene glycol and water at a volume ratio of 1:0.6 to obtain an aqueous polyethylene glycol solution.

S2.3. Soak the pretreated waste wood material in polyethylene glycol aqueous solution, then add 28IU/g laccase, adjust the pH of the solution to 5 with citric acid-sodium citrate buffer solution, and activate the reaction at 35°C 2h; During the activation process, a mixed gas of ammonia/air was introduced at a flow rate of 30 mL/min, and the volume percentage of ammonia in the mixed gas was 10%.

S2.4. Transfer the activation solution of S2.3 into water according to the volume ratio of 1:90, and heat-treat at 130°C for 10s to inactivate laccase; then according to the mass ratio of waste wood raw materials and cationic styrene-acrylic emulsion to 1: 0.6 Add cationic styrene-acrylic emulsion and ball mill to obtain modified nanofiber material.

S3. Mix sodium hydroxide and sodium silicate according to the mass ratio of 1:2 as an alkali stimulator, add it to the tailings sand, mix and vibrate, then place it at 450°C for 2 hours, and then vibrate the material to obtain Activated tailings sand;

S4, uniformly mixing the activated tailings sand with fly ash, expanded slag, and coal gangue powder to obtain a mixture;

S5. Mix the modified nanofibrous material with water evenly, add the mixture, early strength agent and water reducing agent, after mixing evenly, add cement, continue to mix and mix, and obtain the grouting material for filling the soil cave or karst cave.

Example 3

A soil cave or karst cave filling grouting material is prepared from the following raw materials in parts by mass:

240 parts of cement, 80 parts of fly ash, 680 parts of tailings sand, 80 parts of expanded slag, 210 parts of coal gangue powder, 3 parts of modified nanofiber material, 50 parts of additives and 550 parts of water.

The additives include an early strength agent, a water reducer and a base activator, and the mass ratio of the early strength agent, the base activator and the water reducer is 1:1:0.1. The early strength agent is a mixture of sodium sulfite, calcium chloride, and Glauber's salt in a mass ratio of 1:1:2; the water reducer is a polycarboxylate water reducer; the alkali activator is sodium hydroxide and sodium silicate by mass Ratio 1:1 mix.

A method for preparing a grouting material for filling a soil cave or a karst cave, comprising the following steps:

S1. Weigh each raw material according to the ratio;

S2, preparation of modified nanofiber material:

S2.1, cut the corn stalks into small pieces, soak them in a citric acid-sodium citrate buffer solution with a pH of 4 for 12 hours, the amount of the citric acid-sodium citrate buffer solution is to submerge the corn stalks, and then filter. The filter residue was rinsed with distilled water and dried in an oven at 40°C to obtain pretreated waste woody material.

S2.2. Mix polyethylene glycol and water at a volume ratio of 1:0.2 to obtain an aqueous solution of polyethylene glycol.

S2.3. Soak the pretreated waste wood material in aqueous polyethylene glycol solution, then add 18IU/g laccase, adjust the pH of the solution to 4 with citric acid-sodium citrate buffer solution, and activate the reaction at 40°C 1h; during the activation process, a mixed gas of ammonia/air was introduced at a flow rate of 30 mL/min, and the volume percentage of ammonia in the mixed gas was 5%.

S2.4. Transfer the activation solution of S2.3 into water according to the volume ratio of 1:50, and heat-treat at 110°C for 15s to inactivate laccase; then according to the mass ratio of waste wood raw materials and cationic styrene-acrylic emulsion to 1: 0.3 Add cationic styrene-acrylic emulsion and ball mill to obtain modified nanofiber material.

S3. Mix sodium hydroxide and sodium silicate according to the mass ratio of 1:1 as an alkali stimulator, add them to the tailings sand, mix and vibrate and grind, then place them at 350°C for 1 hour, and then vibrate and grind the materials to obtain Activated tailings sand;

S4, uniformly mixing the activated tailings sand with fly ash, expanded slag, and coal gangue powder to obtain a mixture;

S5. Mix the modified nanofibrous material with water evenly, add the mixture, early strength agent and water reducing agent, after mixing evenly, add cement, continue to mix and mix, and obtain the grouting material for filling the soil cave or karst cave.

Comparative example 1

A soil cave or karst cave filling grouting material is prepared from the following raw materials in parts by mass:

300 parts of cement, 90 parts of fly ash, 900 parts of tailings sand, 90 parts of expanded slag, 260 parts of coal gangue powder, 4.5 parts of modified nanofiber material, 100 parts of additives and 700 parts of water.

The additives include an early strength agent, a water reducer and a base activator, and the mass ratio of the early strength agent, the base activator and the water reducer is 1:1:0.2. The early strength agent is a mixture of sodium sulfite, calcium chloride, and Glauber's salt in a mass ratio of 1:1:2.3; the water reducer is a polycarboxylate water reducer; the alkali activator is sodium hydroxide and sodium silicate by mass The ratio is 1:1.5 for mixing.

The preparation method of earth cave or karst cave filling grouting material is basically the same as the method of embodiment 1, and its difference is:

S2.3. Soak the pretreated waste woody material in polyethylene glycol aqueous solution, then add 25IU/g laccase, adjust the pH of the solution to 4.5 with citric acid-sodium citrate buffer solution, and activate the reaction at 40°C 1.5h; During the activation process, air was introduced at a flow rate of 30mL/min.

Comparative example 2

A soil cave or karst cave filling grouting material is prepared from the following raw materials in parts by mass:

300 parts of cement, 90 parts of fly ash, 900 parts of tailings sand, 90 parts of expanded slag, 260 parts of coal gangue powder, 4.5 parts of modified nanofiber material, 100 parts of additives and 700 parts of water.

The additives include an early strength agent, a water reducer and a base activator, and the mass ratio of the early strength agent, the base activator and the water reducer is 1:1:0.2. The early strength agent is a mixture of sodium sulfite, calcium chloride, and Glauber's salt in a mass ratio of 1:1:2.3; the water reducer is a polycarboxylate water reducer; the alkali activator is sodium hydroxide and sodium silicate by mass The ratio is 1:1.5 for mixing.

The preparation method of earth cave or karst cave filling grouting material is basically the same as the method of embodiment 1, and its difference is:

S2.3. Soak the pretreated waste woody material in polyethylene glycol aqueous solution, then add 25IU/g laccase, adjust the pH of the solution to 4.5 with citric acid-sodium citrate buffer solution, and activate the reaction at 40°C 1.5h; During the activation process, a mixed gas of ammonia/air is introduced at a flow rate of 30 mL/min, and the volume percentage of ammonia in the mixed gas is 20%.

Comparative example 3

A soil cave or karst cave filling grouting material is prepared from the following raw materials in parts by mass:

300 parts of cement, 90 parts of fly ash, 900 parts of tailings sand, 90 parts of expanded slag, 260 parts of coal gangue powder, 4.5 parts of modified nanofiber material, 100 parts of additives and 700 parts of water.

The additives include an early strength agent, a water reducer and a base activator, and the mass ratio of the early strength agent, the base activator and the water reducer is 1:1:0.2. The early strength agent is a mixture of sodium sulfite, calcium chloride, and Glauber's salt in a mass ratio of 1:1:2.3; the water reducer is a polycarboxylate water reducer; the alkali activator is sodium hydroxide and sodium silicate by mass The ratio is 1:1.5 for mixing.

The preparation method of earth cave or karst cave filling grouting material is basically the same as the method of embodiment 1, and its difference is:

S2.3. Soak the pretreated waste woody material in polyethylene glycol aqueous solution, then add 25IU/g laccase, adjust the pH of the solution to 4.5 with citric acid-sodium citrate buffer solution, and activate the reaction at 40°C 1.5h; During the activation process, a mixed gas of ammonia/air is introduced at a flow rate of 30 mL/min, and the volume percentage of ammonia in the mixed gas is 30%.

The soil cave or karst cave filling grouting materials of Examples 1-3 and Comparative Examples 1-3 were mixed and filled in molds of the same specification, observed and recorded as shown in Table 1 below.

Table 1 Observation results of mixed filling with grouting materials in soil caves or karst caves

It can be seen from the results in Table 1 that the soil cave or karst cave filling grouting materials prepared in Examples 1-3 of the present invention can effectively improve the overall 28-day compressive strength. Compared with Comparative Examples 1 to 3, Examples 1 to 3 of the present invention can significantly improve the compressive strength and maintain a suitable solidification time by feeding an appropriate amount of ammonia/air mixture, and when the amount of ammonia gas is passed When it is large, it will obviously affect the rheology and apparent viscosity of the mixture, thereby further shortening the setting time. The shortening of solidification time is not conducive to the mixing of raw materials, and has certain restrictions on the promotion of its application.

Inject the soil cave or cave filling grouting materials of Examples 1 to 3 and Comparative Examples 1 to 3 into molds of the same specifications, demould after curing, and obtain test samples. Physical and Mechanical Performance Test Method Standards" for performance testing, the results are shown in Table 2.

Table 2 Performance test results of test samples

It can be seen from the results in Table 2 that, compared with Comparative Example 1, the overall compressive strength and tensile strength of Examples 1 to 3 of the present invention can be significantly improved by injecting an appropriate amount of ammonia gas. Compared with Comparative Examples 2-3, the introduction of excessive ammonia gas will obviously affect the rheology and apparent viscosity of the mixture, and the breaking strength will also be greatly affected. It can be seen that the introduction of ammonia gas can Improve the rheology and apparent viscosity of the mixture, and improve the compressive strength and breaking strength, but the amount of ammonia gas needs to be controlled reasonably. And by observing the fracture surface, it is not obvious that the surface pulverization of the grouting materials for soil cave or karst cave filling in Examples 1 to 3 of the present invention is not obvious. It can be seen that the grouting materials for soil cave or karst cave filling in Examples 1 to 3 of the present invention solve the problem. There is a problem that the filling grouting material is easily pulverized after being broken.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention. Inside.

Claims (9)

1. The soil cave or karst cave filling grouting material is characterized by being prepared from the following raw materials in parts by mass:

240-360 parts of cement, 80-100 parts of fly ash, 680-910 parts of tailing sand, 80-100 parts of expanded slag, 210-280 parts of coal gangue powder, 3-5 parts of modified nanofiber material, 50-120 parts of additive and 550-750 parts of water;

the modified nanofiber material is prepared by the following method:

soaking the pretreated waste wood raw material in a polyethylene glycol aqueous solution, adding laccase, adjusting the pH to 4-5 by using a buffer solution, and then carrying out an activation reaction for 1-2 h at 35-40 ℃; then transferring the activating solution into water, and carrying out heat treatment for 10-15 s at 110-130 ℃; and then adding the cationic styrene-acrylic emulsion, and performing ball milling to obtain the modified nanofiber material.

2. A soil cave or karst cave filling grouting material according to claim 1, characterized in that the additive comprises an early strength agent, a water reducing agent and an alkali activator.

3. The earth cave or karst cave filling grouting material of claim 2, wherein in the additive, the mass ratio of the early strength agent to the alkali activator to the water reducing agent is 1:1:0.1 to 0.3.

4. The earth cave or karst cave filling grouting material of claim 2, wherein the early strength agent is sodium sulfite, calcium chloride and mirabilite according to a mass ratio of 1:1: 2-3;

the water reducing agent is a polycarboxylic acid water reducing agent;

the alkali activator is sodium hydroxide and sodium silicate in a mass ratio of 1:1 to 2.

5. The earth cave or karst cave filling grouting material of claim 1, wherein the polyethylene glycol aqueous solution is prepared by mixing polyethylene glycol and water according to a volume ratio of 1:0.2 to 0.6 percent;

the dosage ratio of the waste wood raw material to the polyethylene glycol aqueous solution is 1g:4 to 8mL.

6. The soil cave or karst cave filling and grouting material of claim 1, wherein the laccase is used in an amount of 18-28 IU/g.

7. The soil cave or karst cave filling and grouting material according to claim 1, wherein the buffer is an acetic acid-sodium acetate buffer, a citric acid-sodium citrate buffer or a citric acid-disodium hydrogen phosphate buffer;

the waste wood raw material is waste wood or waste straw; the waste straw is any one of corn straw, wheat straw and cotton straw;

the pretreatment process of the waste wood raw material comprises the following steps: the waste wood raw materials are crushed and then are placed in a buffer solution for soaking for 8-12 hours, and the wood composite material is obtained after filtration and drying.

8. The cave or karst cave filling and grouting material of claim 1, wherein mixed gas is introduced during the activation reaction of the waste wood raw material, the mixed gas is formed by mixing ammonia gas and air, and the ammonia gas accounts for 5-10% of the mixed gas by volume.

9. A preparation method of a soil cave or karst cave filling grouting material is characterized by comprising the following steps:

s1, weighing the raw materials according to the proportion of claim 1;

s2, mixing sodium hydroxide and sodium silicate according to a mass ratio of 1: 1-2 are added into the tailing sand, mixed and vibrated, then calcined for 1-2 h at 350-450 ℃, and then the materials are vibrated to obtain activated tailing sand;

s3, uniformly mixing the activated tailing sand with the fly ash, the expanded slag and the coal gangue powder to obtain a mixture;

and S4, uniformly mixing the modified nanofiber material with water, adding the mixture, the early strength agent and the water reducing agent, adding cement after uniform mixing, and continuously stirring and mixing to obtain the soil cave or karst cave filling and grouting material.