CN118047588A - Waterproof soil curing agent and preparation method and application method thereof - Google Patents

Abstract

The invention provides a water-resistant soil curing agent, a preparation method and a use method thereof, wherein the water-resistant soil curing agent comprises a component A and a component B, and the component A comprises the following components: 500-700 parts of phosphogypsum; 1 to 5 portions of coke powder; 80-160 parts of fly ash; 10-20 parts of calcium aluminate; 50-100 parts of silicate cement clinker; 100-200 parts of steel slag powder; 100-200 parts of mineral powder; 5-10 parts of quicklime; 5-10 parts of sodium sulfate; 2-8 parts of calcined alunite; 1-5 parts of instant solid water glass; the component B comprises: 10-90 parts of hydroxyl silicone oil emulsion; 5-20 parts of methyl hydrogen silicone oil emulsion; 15-30 parts of epoxy polyamine addition compound; 5-12 parts of zinc acetate; 1-5 parts of zirconium hydroxide; 1-5 parts of triethanolamine; 1-4 parts of a coupling agent; 1-5 parts of wetting agent; 600-850 parts of water. The water-resistant soil curing agent disclosed by the invention can improve the compactness of soil, has a good curing effect on heavy metals in soil, enhances the compressive strength of the soil, and ensures that the soil has good water stability and good water resistance.

Description

A water-resistant soil solidifying agent and its preparation method and use method

Technical Field

The invention relates to the technical field of solid waste resource utilization and soil solidification, and in particular to a water-resistant soil solidifier and a preparation method and a use method thereof.

Background technique

Soil stabilizer is the abbreviation of soil solidification admixture. It is a new energy-saving and environmentally friendly engineering material synthesized from a variety of inorganic and organic materials to solidify various types of soil. For the soil to be reinforced, according to the physical and chemical properties of the soil, it only needs to add a certain amount of solidifier, mix well, and compact it to achieve the required performance indicators.

Soil solidifiers cover a wide range of fields and are used in building foundations, dam slope protection, tidal flat silt, dust and sand control, industrial sludge solidification and other fields. They can not only achieve the effect of reinforcement and strengthening, but also effectively stabilize pollutants to prevent infiltration and pollution of the environment.

Soil solidifiers can be divided into powder and liquid in terms of form, and can be divided into three categories in terms of composition: inorganic, organic, and bio-enzyme. Inorganic soil solidifiers are mainly powder-type, including lime cement solidifiers, slag silicate solidifiers, etc., which have good stability and low cost, but are prone to cracking and have insufficient early strength; organic soil solidifiers are mainly polymer liquid solidifiers based on macromolecules, with small dosages and good water resistance, but limited scope of use and easy aging; bio-enzyme solidifiers are biological solidifiers, which have obvious solidification effects on high plastic clay, but have high preparation costs and are easily degraded, thus affecting their lifespan. Most of the currently known solidifiers have the problem of poor water resistance, and the soil solidifiers that have been constructed are not water stable enough, especially liquid solidifiers that cannot consolidate foundation soil after being soaked in rainwater for a long time.

Based on comprehensive performance considerations, high water resistance is an important indicator for maintaining strength and durability of curing agents while seeking high strength performance of curing agents. Achieving satisfaction in strength, water resistance and economic efficiency including material price, waste utilization and construction convenience with cheap renewable raw materials such as biomass is an urgent task in the current development of soil curing agents. Among them, organic (especially biomass organic matter) inorganic composite curing agents have advantages in areas with high requirements for strength and durability, such as roads and riverbank projects.

Silicone is a new type of chemical product with many varieties, excellent performance and wide application, known as "industrial MSG". Various silanes, siloxane intermediates and silicone oils, silicone rubbers, silicone resins (including their secondary processed products), coupling agents and other products made from them have been widely used in the electronics, construction, automobile, textile, light industry, cosmetics, medical, food and other industries, and have played a positive role. It has been proved in practice that silicone emulsion has good water resistance, and adding a small amount of silicone emulsion can significantly improve the water stability of soil.

Phosphogypsum is an industrial solid waste produced by wet phosphoric acid production. It contains certain organic phosphorus and inorganic phosphorus residues, which make phosphogypsum acidic. The production of 1 ton of phosphoric acid emits about 4 to 5 tons of phosphogypsum. At present, the stockpile of phosphogypsum in my country is about 600 million tons, and the storage yard is close to saturation. However, the utilization rate of bulk solid wastes such as phosphogypsum and phosphate slag is less than 10%. The large stockpile and low consumption cause a large waste of land resources, which not only threatens environmental safety, but also easily causes safety accidents such as landslides and mudslides, causing serious casualties and property losses. If the management and control are not good, the phosphorus, sulfur, heavy metals, etc. in the phosphogypsum will also infiltrate and flow out of the storage yard with rainwater, causing certain pollution to the surrounding soil, groundwater, rivers, etc. The low activity and slow hydration characteristics of the original phosphogypsum limit the expansion of its resource utilization. This situation can be improved through activity excitation. The main activity excitation methods are physical excitation, thermal excitation and chemical excitation. Physical excitation is to use mechanical methods to increase the fineness of phosphogypsum, thereby increasing the activity of phosphogypsum; thermal excitation is to provide heat to phosphogypsum to increase the activity of phosphogypsum; chemical excitation is to introduce a small amount of activator to participate in and accelerate the hydration reaction of phosphogypsum materials under alkaline conditions. The current application scenarios of phosphogypsum include: as a raw material for cement, sulfuric acid, and building gypsum; as a retarder; and to prepare cementitious materials together with other industrial wastes, etc. However, the consumption of phosphogypsum is low, and there are problems such as high cost and poor water resistance.

Summary of the invention

The purpose of the present invention is to overcome the above-mentioned deficiencies of the prior art and to provide a water-resistant soil solidifying agent and a preparation method and a use method thereof.

To achieve the above-mentioned object of the invention, in a first aspect, the present invention provides a water-resistant soil solidifying agent, comprising a component A and a component B, wherein the component A and the component B respectively comprise the following raw materials in parts by weight:

The component A comprises the following raw materials in parts by weight: 500-700 parts of phosphogypsum; 1-5 parts of coke powder; 80-160 parts of fly ash; 10-20 parts of calcium aluminate; 50-100 parts of Portland cement clinker; 100-200 parts of steel slag powder; 100-200 parts of mineral powder; 5-10 parts of quicklime; 5-10 parts of sodium sulfate; 2-8 parts of calcined alum stone; 1-5 parts of instant solid water glass;

The component B comprises the following raw materials in parts by weight: 10 to 90 parts of hydroxy silicone oil emulsion; 5 to 20 parts of methyl hydrogen silicone oil emulsion; 15 to 30 parts of epoxy polyamine adduct; 5 to 12 parts of zinc acetate; 1 to 5 parts of zirconium hydroxide; 1 to 5 parts of triethanolammonium; 1 to 4 parts of coupling agent; 1 to 5 parts of wetting agent; and 600 to 850 parts of water.

In one embodiment, the composition of the phosphogypsum includes CaS0 ₄ ·2H ₂ 0, P ₂ O ₅ , MgO, Fe ₂ O ₃ , Al ₂ O ₃ and CaO;

The coke powder is a finely ground powder of refined coking coal with a carbon content of more than 90% for metallurgy, with a fineness of 280 mesh to 400 mesh;

The steel slag powder has a specific surface area of 400-800 m2/kg, a mesh size of 380-600 meshes, and its components include Al ₂ O ₃ , SiO ₂ , CaO, Fe ₂ O ₃ , SO ₃ , C ₄ A ₃ , C ₂ S and C ₄ AF;

The slag powder has an iron oxide content of 50% to 60% and a silicon oxide content of 30% to 40%;

The components of the instant solid water glass include 2.5% to 3.8% of instant solid sodium silicate.

In one embodiment, the hydroxy silicone oil emulsion has a molar mass of 30 to 60 g/mol and a pH value of 5.5 to 7;

The methyl hydrogen silicone oil emulsion has a viscosity of less than 50 mm ² /s, a pH value of 3 to 4, and a hydrogen mass fraction of 1 to 1.5%;

The zinc acetate is zinc acetate dihydrate, containing 2 molecules of crystal water;

The zirconium hydroxide is of industrial grade and contains 8 molecules of crystal water;

The wetting agent is silicone;

The water is deionized water.

In a second aspect, the present invention provides a method for preparing a water-resistant soil solidifying agent, comprising:

Step 1: flotation and impurity removal, solid-liquid separation and drying are performed on the original phosphogypsum to obtain the impurity-removed phosphogypsum;

Step 2: fully mixing the phosphogypsum after the impurity removal treatment with coke powder, sodium sulfate and calcined alum stone to obtain a first mixed material;

Step 3: irradiating the first mixed material with a microwave generator to obtain a first mixed material after microwave irradiation;

Step 4: Mix the first mixture after microwave irradiation with silicate cement clinker, steel slag powder, mineral powder and fly ash in proportion and send them to an ultrafine pulverizer for pulverization to obtain a second mixture;

Step 5: Mix and grind the second mixed material with calcium aluminate, quicklime and instant solid water glass to obtain the A component;

Step 6: Add hydroxy silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolammonium, coupling agent and wetting agent to water in sequence, and stir continuously at room temperature to dissolve them to obtain the B component.

In one embodiment, in the step three, a microwave generator of 300 MHz to 945 GHz is used to irradiate the first mixed material at 145° C. for 20 to 40 minutes to obtain a first mixed material after microwave irradiation.

In one embodiment, in the step 4, the first mixture after microwave irradiation is mixed with silicate cement clinker, steel slag powder, mineral powder and fly ash in proportion and sent to an ultra-fine pulverizer to be crushed to 380-480 meshes to obtain a second mixture;

In the step six, hydroxy silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolammonium, coupling agent and wetting agent are added to water in sequence, and stirred continuously at 100-200 r/min at room temperature to dissolve them, and stirring is continued for 30 minutes to obtain the B component.

In a third aspect, the present invention provides an application of a water-resistant soil solidifier in water conservancy slope protection, tidal flat solidification, road base and subbase, grouting materials and construction environments.

In a fourth aspect, the present invention provides a method for using a water-resistant soil solidifier, comprising:

The component A is first mixed with the solidified object, and after the mixing, the component B is added with water for a second mixing to obtain a mixture, and the mixture is filled or compacted, and then cured to obtain solidified soil.

In one embodiment, the weight ratio of component A of the water-resistant soil solidifier to the solidified object is 1:9 to 3:7, and the amount of component B of the water-resistant soil solidifier is 2 to 10% of the weight of the solidified object; in the step of adding the component B and water for the second mixing after mixing, the amount of water is 7 to 55% of the weight of the solidified object.

In one embodiment, the first mixing time is 2 to 3 minutes, and the second mixing time is 3 to 5 minutes.

The advantages and beneficial effects of the present invention over the prior art are as follows:

(1) In the present invention, phosphogypsum is a complex crystal of multiple components. The preparation method provided by the present invention adopts a microwave-physical-chemical composite excitation method to stabilize _the soluble _P2O5 and Fe2 ⁺ in the phosphogypsum, reduce the harmful components therein into crystals to become harmless stable materials, and are wrapped by a gelling agent.

(2) When microwave irradiation is used, the various chemical components that make up phosphogypsum have different properties, and their heating rates in the microwave field are different. A significant local temperature difference will be formed between the minerals that absorb microwaves, partially absorb microwaves, and do not absorb microwaves. On the one hand, thermal stress will be generated between the minerals, which will promote the formation of cracks on the interface between the minerals. At the same time, it will effectively promote the monomer dissociation of the microwave-absorbing minerals and increase the effective reaction area of the microwave-absorbing minerals. On the other hand, the phosphogypsum will be dehydrated during the heating process, resulting in crystal transformation, phase change or chemical reaction.

(3) In the present invention, the organosilicon component B participates in the reaction together with the component A, and at the same time forms a layer of organosilicon film on the surface of the solidified soil, which not only effectively improves the curing performance of the soil solidifier, but also effectively improves the water resistance of the soil after curing, prolongs the service life, can reduce social costs, save resources, and improve soil curing efficiency. It is suitable for soil curing treatment of roads, airports and farmland slopes that are subject to natural rainwater erosion.

Detailed ways

In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

In a first aspect, the present invention provides a water-resistant soil solidifying agent, comprising a component A and a component B, wherein the component A and the component B respectively comprise the following raw materials in parts by weight:

The component A comprises the following raw materials in parts by weight: 500-700 parts of phosphogypsum; 1-5 parts of coke powder; 80-160 parts of fly ash; 10-20 parts of calcium aluminate; 50-100 parts of Portland cement clinker; 100-200 parts of steel slag powder; 100-200 parts of mineral powder; 5-10 parts of quicklime; 5-10 parts of sodium sulfate; 2-8 parts of calcined alum stone; 1-5 parts of instant solid water glass;

The component B comprises the following raw materials in parts by weight: 10 to 90 parts of hydroxy silicone oil emulsion; 5 to 20 parts of methyl hydrogen silicone oil emulsion; 15 to 30 parts of epoxy polyamine adduct; 5 to 12 parts of zinc acetate; 1 to 5 parts of zirconium hydroxide; 1 to 5 parts of triethanolammonium; 1 to 4 parts of coupling agent; 1 to 5 parts of wetting agent; and 600 to 850 parts of water.

Furthermore, the composition of the phosphogypsum includes CaS0 ₄ ·2H ₂ 0, P ₂ O ₅ , MgO, Fe ₂ O ₃ , Al ₂ O ₃ and CaO; the phosphogypsum is an ultrafine acid waste produced by phosphorus chemical industry, and its main components are CaS0 ₄ ·2H ₂ 0, P ₂ O ₅ , MgO, Fe ₂ O ₃ , Al ₂ O ₃ and CaO, etc., which can provide calcium ions and sulfate ions for soil solidifiers;

The coke powder is a finely ground powder of refined coking coal with a carbon content of more than 90% for metallurgy, with a fineness of 280-400 meshes, and is a wave absorbing heating material;

The fly ash is the fine ash collected from the flue gas after coal combustion in power plants. Fly ash is the main solid waste discharged from coal-fired power plants, has a volcanic ash effect, and is the main component of calcium silicate hydrate.

The calcium aluminate is specifically commercially available high-alumina cement, the main chemical components of which are Al ₂ O ₃ and CaO. It has strong activity and provides an aluminum source for the cementitious material.

The Portland cement clinker is an unprocessed and finely ground finished product produced by a cement plant, which provides active activating substances for the cementitious material;

The steel slag powder is steel slag obtained by grinding waste slag from steelmaking in a steel plant after being heated and stuffed. The steel slag powder has a specific surface area of 400-800 m ² /kg and a mesh size of 380-600 meshes. Its components include Al ₂ O ₃ , SiO ₂ , CaO, Fe ₂ O ₃ , SO ₃ , C ₄ A ₃ , C ₂ S and C ₄ AF, etc.

The slag powder is blast furnace slag, which refers to a waste produced in the iron-making process, and its main components are iron oxide and silicon oxide. Among them, the content of iron oxide is 50% to 60%, and the content of silicon oxide is 30% to 40%. In addition, the slag also contains a small amount of impurities such as aluminum oxide, calcium oxide, and magnesium oxide. The ground slag is ground to more than 400 mesh, and its active calcium, silicon, aluminum and other inorganic substances are greater than 30%, and the activity index is greater than 95%. The silicon oxide in the blast furnace slag is an active inorganic compound, which provides the system with active silicon with volcanic ash effect;

The quicklime is commercially available CaO. As an alkaline activator, the addition of quicklime can adjust the alkalinity of the anhydrous gypsum slurry and stimulate the activity of the slag. After the quicklime is added, the lime in the anhydrous gypsum slurry first reacts with water and quickly hydrates to form Ca(OH) ₂ , creating an alkaline medium environment for the entire system, followed by the formation of dihydrate gypsum. The presence of the alkaline medium stimulates the potential activity of the slag to generate calcium sulfonate crystals and hydrated calcium silicate gel with higher strength and stability than dihydrate gypsum and lower solubility in water. These newly added products continuously fill and wrap in the structure of dihydrate gypsum and anhydrous gypsum, making the overall structure denser, thereby improving the early and later strengths;

The sodium sulfate is commercially available sodium sulfate. The addition of sodium sulfate (Na ₂ SO ₄ ) can accelerate the formation of supersaturation of anhydrous gypsum and reduce its crystallization activation energy, accelerate crystallization, and significantly improve the hydration rate. Therefore, the addition of sodium sulfate can significantly improve the early strength of anhydrous gypsum hardening body;

The calcined alunite is commercially available and is a natural ore mainly containing potassium aluminum sulfate double salt. It is calcined and the required effective component is aluminum oxide. The higher the sulfur trioxide content, the better its activated water property. Alunite forms ettringite under the stimulation of alkali-sulfate, so that the strength of cement paste is well developed. After calcination, dehydration and activation, alunite has high solubility and the ability to react with cement hydrates. It can quickly interact with gypsum to form ettringite, thereby further accelerating and deepening the hydration and hardening of cement.

The instant solid water glass mainly contains 2.5% to 3.8% of instant solid sodium silicate, which is an early strong alkalinity activator in the system. The function of the water glass is that the water glass reacts with anhydrous gypsum particles to precipitate Ca(OH) ₂ , making the anhydrous gypsum slurry alkaline, increasing the dissolution amount of anhydrous gypsum, generating more dihydrate gypsum, and having a significant stimulating effect on accelerating the hydration of anhydrous gypsum.

Furthermore, the hydroxy silicone oil emulsion (hydroxy emulsion) has a molar mass of 30 to 60 g/mol and a pH value of 5.5 to 7, is an emulsion polymerization, and is the main component for forming an organic silicon film;

The methyl hydrogenated silicone oil emulsion (hydrogenated emulsion) has a viscosity of <50 mm2/s, a pH value of 3 to 4, a hydrogen mass fraction of 1 to 1.5%, is mechanically emulsified, and can form an organic silicon film crosslinking agent;

The epoxy polyamine adduct is an industrial product, and the synthesis method is to add an excess of amine to a single-component epoxy synthesis system, which can be used as an emulsion stabilizer and increase the adhesion of the silicone film;

The zinc acetate is zinc acetate dihydrate, contains 2 molecules of crystal water, is grade three, and is used as a hydrolysis condensation catalyst and filler.

The zirconium hydroxide is industrial grade and contains 8 molecules of crystal water, which is deposited in the soil gap, promotes the directional arrangement of silicon-oxygen bonds, and increases the waterproof effect;

The triethanolammonium acts as a hydrolysis condensation catalyst;

The coupling agent is KH560, which can increase the compatibility of each component;

The wetting agent is organic silicon H140, which can improve the wetting and dispersibility of the material and has a water-reducing effect;

The water is deionized water, which is used as a diluent for the B component.

In a second aspect, the present invention provides a method for preparing a water-resistant soil solidifying agent, comprising:

Step 1: flotation and impurity removal, solid-liquid separation and drying are performed on the phosphogypsum to obtain the impurity-removed phosphogypsum;

Step 2: fully mixing the phosphogypsum after the impurity removal treatment with coke powder, sodium sulfate and calcined alum stone to obtain a first mixed material;

Step 3: irradiating the first mixed material with a microwave generator to obtain a first mixed material after microwave irradiation;

Step 4: Mix the first mixture after microwave irradiation with silicate cement clinker, steel slag powder, mineral powder and fly ash in proportion and send them to an ultrafine pulverizer for pulverization to obtain a second mixture;

Step 5: Mix and grind the second mixed material with calcium aluminate, quicklime and instant solid water glass to obtain the A component;

Step 6: Add hydroxy silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolammonium, coupling agent, and wetting agent to water in sequence, and stir continuously at 100-200 r/min at room temperature to dissolve them, and continue stirring for 30 minutes to obtain the B component.

Furthermore, in the step three, a microwave generator of 300 MHz to 945 GHz is used to irradiate the first mixed material at 145° C. for 20 to 40 minutes to obtain a first mixed material after microwave irradiation.

Furthermore, in the step 4, the first mixture after microwave irradiation is mixed with silicate cement clinker, steel slag powder, mineral powder and fly ash in proportion and sent to an ultra-fine pulverizer to be crushed to 380-480 meshes to obtain a second mixture;

In the step six, hydroxy silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolammonium, coupling agent and wetting agent are added to water in sequence, and stirred continuously at 100-200 r/min at room temperature to dissolve them, and stirring is continued for 30 minutes to obtain the B component.

Microwave irradiation stimulates the activity of minerals, generates heat through internal vibration of materials, promotes the formation of cracks at the mineral interface, increases the specific surface area of minerals, and facilitates adsorption, bonding, and reaction with soil particles, thereby enhancing the solidification of soil. Microwave irradiation can also dehydrate phosphogypsum to undergo crystal transformation and phase change reaction, converting it into hemihydrate gypsum and anhydrous gypsum in large quantities, which helps to improve the solidification of soil.

In a third aspect, the present invention provides the use of a water-resistant soil solidifier in water conservancy slope protection, beach solidification, road base and subbase, grouting materials and construction environments.

The above-mentioned water-resistant soil solidifier can be applied to the fields of water conservancy slope protection, tidal flat solidification, road base and subbase, grouting material and building environment, and has the characteristics of simple construction, excellent performance, low cost and environmental friendliness.

In a fourth aspect, the present invention provides a method for using a water-resistant soil solidifier, comprising:

Step 1: first mixing the component A with the solidified object, and then adding the component B and water to perform a second mixing to obtain a mixture;

The specific step 1 is: firstly, the component A is mixed with the solidified material for a first time for 2 to 3 minutes, and then the component B is added with an appropriate amount of water for a second mixing, and the mixture is mixed for 3 to 5 minutes to obtain a mixture.

Step 2: Fill or compact the mixture, and then perform curing to obtain solidified soil.

Step two is as follows: when used for sand solidification, the mixture is injected into a 7.07cm*7.07cm*7.07cm mold and vibrated, the mold is removed after 24 hours, and then it is cured in a standard curing box for 28 days, and a compression testing machine is used for strength testing; and or for road base and bottom layers, the mixture is filled into a cylindrical steel mold, compacted and formed using a press, and after demolding, it is sealed with plastic wrap and placed in a standard curing box for 7 days, and a 7-day unconfined compressive strength test is performed using a compression testing machine.

Furthermore, in step one, the weight ratio of component A of the water-resistant soil solidifier to the solidified object is 1:9 to 3:7, and the amount of component B of the water-resistant soil solidifier is 2 to 10% of the weight of the solidified object; in the step of adding the component B and water for the second mixing after mixing, the amount of water is 7 to 55% of the weight of the solidified object.

The positive effect of controlling the amount of component A and component B: within this range, the proportion of the curing agent can be adjusted according to the construction strength requirements. If the content of the water-resistant soil curing agent is too high, it will cause a certain degree of increase in the curing cost, and waste resources when the strength index requirement is seriously exceeded; if the content of the water-resistant soil curing agent is too low, it will not be able to meet the curing strength index requirement to a certain extent. Specifically, the weight ratio of component A to the cured product is 1:9 to 3:7, for example, it can be 1:9, 15:85, 2:8, 25:75, 3:7, etc., and the amount of component B is 2 to 10% of the weight of the cured product, for example, it can be 2%, 4%, 6%, 8%, 10%.

The positive effect of controlling the amount of water: the moisture content is determined within this range according to the fluidity index of the mixture during construction. If the water content is too high, the setting time of the solidified soil will be prolonged and the compressive strength will be reduced to a certain extent; if the water content is too low, the soil solidifier will not be fully hydrated to a certain extent, reducing the curing effect. Specifically, the amount of water is 7-55% of the weight of the solidified material, for example, 7%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%.

The present invention has been tested for many times, and some test results are now cited as references to further describe the invention in detail, and the following is a detailed description in conjunction with specific embodiments.

Example 1

In parts by weight, 800 parts of phosphogypsum, 4 parts of coke powder, 10 parts of sodium sulfate, and 8 parts of calcined alum stone are fully stirred at 75 r/min for 5 minutes, irradiated at 145°C for 20 to 40 minutes using a 5.0 kW, 945 MHz microwave generator, and then mixed with 50 parts of silicate cement clinker, 100 parts of steel slag powder, 100 parts of mineral powder, and 150 parts of fly ash. The mixture is crushed to 380 to 400 meshes, and then mixed with 20 parts of calcium aluminate, 10 parts of quicklime and 5 parts of instant solid water glass and ground to obtain component A.

In parts by weight, add 70 parts of hydroxy silicone oil emulsion (hydroxy emulsion), 18 parts of methyl hydrogen silicone oil emulsion (hydrogen emulsion), 29 parts of epoxy polyamine adduct, 11 parts of zinc acetate, 5 parts of zirconium hydroxide, 4 parts of triethanolammonium, 3 parts of coupling agent, and 5 parts of wetting agent to 800 parts of water, and stir continuously at 100 r/min at room temperature to dissolve them. Stir continuously for 30 minutes to obtain component B.

Example 2

In parts by weight, 600 parts of phosphogypsum, 2 parts of coke powder, 8 parts of sodium sulfate, and 6 parts of calcined alum stone are fully stirred at 75 r/min for 5 minutes, irradiated at 145°C for 20-40 minutes using a 5.0 kW, 945 MHz microwave generator, and then mixed with 60 parts of silicate cement clinker, 150 parts of steel slag powder, 150 parts of mineral powder, and 100 parts of fly ash. The mixture is crushed to 380-400 meshes, and then mixed with 16 parts of calcium aluminate, 8 parts of quicklime and 4 parts of instant solid water glass and ground to obtain component A.

In parts by weight, add 70 parts of hydroxy silicone oil emulsion (hydroxy emulsion), 18 parts of methyl hydrogen silicone oil emulsion (hydrogen emulsion), 29 parts of epoxy polyamine adduct, 11 parts of zinc acetate, 5 parts of zirconium hydroxide, 4 parts of triethanolammonium, 3 parts of coupling agent, and 5 parts of wetting agent to 800 parts of water, and stir continuously at 100 r/min at room temperature to dissolve them. Stir continuously for 30 minutes to obtain component B.

Example 3

In parts by weight, 500 parts of phosphogypsum, 2 parts of coke powder, 6 parts of sodium sulfate, and 4 parts of calcined alum stone are fully stirred at 75 r/min for 5 minutes, irradiated at 145°C for 20 to 40 minutes using a 5.0 kW, 945 MHz microwave generator, and then mixed with 80 parts of silicate cement clinker, 200 parts of steel slag powder, 200 parts of mineral powder, and 100 parts of fly ash. The mixture is crushed to 380 to 400 meshes, and then mixed with 12 parts of calcium aluminate, 6 parts of quicklime and 2 parts of instant solid water glass and ground to obtain component A.

In parts by weight, add 70 parts of hydroxy silicone oil emulsion (hydroxy emulsion), 18 parts of methyl hydrogen silicone oil emulsion (hydrogen emulsion), 29 parts of epoxy polyamine adduct, 11 parts of zinc acetate, 5 parts of zirconium hydroxide, 4 parts of triethanolammonium, 3 parts of coupling agent, and 5 parts of wetting agent to 800 parts of water, and stir continuously at 100 r/min at room temperature to dissolve them. Stir continuously for 30 minutes to obtain component B.

Application Example 1-11

According to Table 1, the water-resistant soil solidifier obtained in Examples 1-3 and red clay were molded into test pieces according to different weight ratios and different water-to-material ratios, and immersed in water on the last day of the curing age. Dry hard water-stable test pieces and fluidized solidified soil test pieces were molded according to different water-to-material ratios. The specific steps are as follows:

The component A of the water-resistant soil solidifier obtained in Example 1-3 is first mixed with red clay, and after mixing, the component B is added and mixed with water for a second time to obtain a mixture, and the mixture is filled or compacted, and then cured, and immersed in water on the last day of the curing age. This process is used as Application Example 1-9, and dry hard water-stable specimens and fluidized solidified soil specimens are formed according to different water-to-material ratios. The water-to-material ratio refers to the ratio of the total weight of water to solid materials, and the material in the water-to-material ratio refers to the total weight of the component A of the water-resistant soil solidifier and the red clay.

The component B in any one of Example 1, Example 2 or Example 3 is mixed with red clay and water for a second time to obtain a mixture, and the mixture is filled or compacted, then cured, and immersed in water on the last day of the curing age. This process is used as Application Example 10. The water-to-material ratio refers to the ratio of the total weight of water to the total weight of solid materials, and the material in the water-to-material ratio refers to the total weight of component A of the water-resistant soil solidifier and the red clay.

Cement and red clay are first mixed, and then mixed with water to obtain a mixture, the mixture is compacted, and then cured, and soaked in water on the last day of the curing age. This process is used as Application Example 11. The weight ratio of cement to red clay in the first mixture is 3:7. The water-to-material ratio refers to the ratio of the total weight of water to solid materials, and the material in the water-to-material ratio refers to the sum of the weight of component A of the water-resistant soil solidifier and the red clay.

Table 1 Usage and application of water-resistant soil stabilizer

Table 2 Performance test results of water-resistant soil stabilizer applied to red clay

The results of the performance test of the water-resistant soil solidifier applied to red clay are shown in Table 2. It can be seen that the water-resistant soil solidifier provided in the embodiment of the present application has a good solidification effect, and the compressive strength of 28d immersion in red clay can reach 1-4MPa. The comparison of the results of Application Example 1 and Application Example 2, Application Example 3 and Application Example 4, and Application Example 5 and Application Example 6 shows that as the dosage of component A of the water-resistant soil solidifier increases, the solidification effect of the red clay is better. The comparison of the results of Application Examples 1-6 and Application Examples 7-9 shows that the fluidized solidified red clay has better compressive strength and water resistance than the dry hard solidified red clay.

Application Examples 12-15

According to Table 3, the component A obtained in Examples 1-3 was mixed with the original phosphogypsum in a weight ratio of 3:7, and then 4% by weight of the component B was added to form a dry hard water-stabilized specimen for an unconfined compressive strength test, and then immersed in water on the last day of the curing age. The specific steps are as follows:

The component A of the water-resistant soil solidifier obtained in Examples 1-3 is first mixed with the original phosphogypsum in a weight ratio of 3:7, and after mixing, the component B is added with water for a second mixing to obtain a mixture. The mixture is compacted and then cured. The dry hard water-stabilized specimens are formed for an unconfined compressive strength test and immersed in water on the last day of the curing age. This process is used as Application Examples 12-14. The water-to-material ratio refers to the ratio of the total weight of water to the total weight of solid materials, and the material in the water-to-material ratio refers to the total weight of the component A of the water-resistant soil solidifier and the original phosphogypsum.

Cement and undisturbed phosphogypsum are first mixed, and then mixed with water to obtain a mixture, the mixture is compacted, and then cured, and immersed in water on the last day of the curing age. This process is used as Application Example 15. The weight ratio of cement to undisturbed phosphogypsum in the first mixture is 3:7. The water-to-material ratio refers to the ratio of the total weight of water to solid materials, and the material in the water-to-material ratio refers to the total weight of component A of the water-resistant soil solidifier and the original phosphogypsum.

Table 3 Water-resistant soil solidifier applied to original phosphogypsum usage

Table 4 Performance test results of water-resistant soil solidifier applied to original phosphogypsum

The performance test results of the water-resistant soil solidifier applied to the original phosphogypsum are shown in Table 4. It can be seen that the water-resistant soil solidifier provided in the embodiment of the present application has a good curing effect. It can be applied to the original phosphogypsum to cure the 28d immersion compressive strength of 14-16MPa. If it is applied to the road base and subbase, it can meet the index requirements of 3.0-5.0MPa for heavy traffic grades of secondary and lower highways. It can be seen from Application Examples 11 and 15 that the application effect of the water-resistant soil solidifier provided by the present invention is similar to that of cement, but the water-resistant soil solidifier provided in the embodiment of the present invention is all prepared from industrial solid waste, which has the advantage of low cost, and realizes the resource utilization of industrial solid waste, and has good environmental and social benefits.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The waterproof soil curing agent is characterized by comprising a component A and a component B, wherein the component A and the component B respectively comprise the following raw materials in parts by weight:

The component A comprises the following raw materials in parts by weight: 500-700 parts of phosphogypsum; 1 to 5 portions of coke powder; 80-160 parts of fly ash; 10-20 parts of calcium aluminate; 50-100 parts of silicate cement clinker; 100-200 parts of steel slag powder; 100-200 parts of mineral powder; 5-10 parts of quicklime; 5-10 parts of sodium sulfate; 2-8 parts of calcined alunite; 1-5 parts of instant solid water glass;

The component B comprises the following raw materials in parts by weight: 10-90 parts of hydroxyl silicone oil emulsion; 5-20 parts of methyl hydrogen silicone oil emulsion; 15-30 parts of epoxy polyamine addition compound; 5-12 parts of zinc acetate; 1-5 parts of zirconium hydroxide; 1-5 parts of triethanolamine; 1-4 parts of a coupling agent; 1-5 parts of wetting agent; 600-850 parts of water.

2. The water-resistant soil stabilizer according to claim 1, wherein:

The raw phosphogypsum comprises CaS0 ₄·2H₂0、P₂O₅、MgO、Fe₂O₃、Al₂O₃ and CaO;

the coke powder is refined coke powder with carbon content more than 90% for metallurgy, and the fineness is 280-400 meshes;

The specific surface area of the steel slag powder is 400-800 m2/kg, the mesh number is 380-600 meshes, and the components of the steel slag powder comprise Al₂O₃、SiO₂、CaO、Fe₂O₃、SO₃、C₄A₃、C₂S and C ₄ AF;

The content of ferric oxide in the slag powder is 50% -60%, and the content of silicon oxide is 30% -40%;

The instant solid sodium silicate comprises 2.5% -3.8% of instant solid sodium silicate.

3. The water-resistant soil stabilizer according to claim 1, wherein:

The molar mass of the hydroxyl silicone oil emulsion is 30-60 g/mol, and the pH value is 5.5-7;

The viscosity of the methyl hydrogen-containing silicone oil emulsion is less than 50mm ²/s, the pH value is 3-4, and the mass fraction of hydrogen is 1-1.5%;

The zinc acetate is zinc acetate dihydrate and contains 2 molecules of crystal water;

The zirconium hydroxide is of industrial grade and contains 8 molecular crystal water;

the wetting agent is organic silicon;

The water is deionized water.

4. A method of preparing a water resistant soil hardener as claimed in any one of claims 1 to 3, comprising:

Step one: performing flotation impurity removal, solid-liquid separation and drying treatment on phosphogypsum to obtain phosphogypsum after the impurity removal treatment;

Step two: fully mixing phosphogypsum after the impurity removal treatment with coke powder, sodium sulfate and calcined alunite to obtain a first mixture;

step three: irradiating the first mixture by adopting a microwave generator to obtain a first mixture after microwave irradiation;

Step four: mixing the first mixture subjected to microwave irradiation with silicate cement clinker, steel slag powder, mineral powder and fly ash according to a proportion, and conveying the mixture to an ultrafine pulverizer for pulverizing to obtain a second mixture;

step five: mixing and overgrinding the second mixture with calcium aluminate, quicklime and instant solid water glass to obtain the component A;

Step six: sequentially adding hydroxyl silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolamine, a coupling agent and a wetting agent into water, and continuously stirring at room temperature to dissolve the components to obtain the component B.

5. The method for preparing the water-tolerant soil stabilizer according to claim 4, wherein in the third step, a microwave generator of 300 MHz-945 GHz is adopted to irradiate the first mixture for 20-40 min at 145 ℃ to obtain a first mixture after microwave irradiation.

6. The method for preparing the water-resistant soil curing agent according to claim 4, wherein in the fourth step, the first mixture after microwave irradiation is mixed with silicate cement clinker, steel slag powder, mineral powder and fly ash according to a proportion and sent to an ultrafine pulverizer to be pulverized into 380-480 meshes to obtain a second mixture;

Sequentially adding hydroxyl silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolamine, coupling agent and wetting agent into water, continuously stirring at room temperature for dissolving at 100-200r/min, and continuously stirring for 30 minutes to obtain the component B.

7. The application of the water-resistant soil curing agent prepared by the preparation method of the water-resistant soil curing agent according to claim 4, which is characterized by being applied to water conservancy revetments, beach curing, road base and subbase, grouting materials and building environments.

8. The method for using the water-resistant soil curing agent prepared by the preparation method of the water-resistant soil curing agent according to claim 4, which is characterized by comprising the following steps:

and (3) carrying out first mixing on the component A and the cured object, adding the component B and water after mixing, carrying out second mixing to obtain a mixture, filling or compacting the mixture, and curing to obtain the cured soil.

9. The method of using according to claim 8, wherein the weight ratio of the a component of the water-resistant soil hardener to the cured product is 1:9-3:7, and the B component of the water-resistant soil hardener is used in an amount of 2-10% of the weight of the cured product; and in the step of adding the B component and water for second mixing after mixing, the water is used in an amount of 7-55% by weight of the cured object.

10. The method of claim 8, wherein the first mixing is for a period of 2 to 3 minutes and the second mixing is for a period of 3 to 5 minutes.