A water-resistant soil stabilizer and methods of making and using the same

Abstract

This invention provides a water-resistant soil stabilizer, its preparation method, and its application method. The water-resistant soil stabilizer includes component A and component B. Component A includes: 500-700 parts phosphogypsum; 1-5 parts coke powder; 80-160 parts fly ash; 10-20 parts calcium aluminate; 50-100 parts silicate cement clinker; 100-200 parts steel slag powder; 100-200 parts mineral powder; 5-10 parts quicklime; 5-10 parts sodium sulfate; 2-8 parts calcined alunite; and 1-5 parts fast-dissolving solid water glass. Component B includes: 10-90 parts hydroxyl silicone oil emulsion; 5-20 parts methyl hydrogen silicone oil emulsion; 15-30 parts epoxy polyamine adduct; 5-12 parts zinc acetate; 1-5 parts zirconium hydroxide; 1-5 parts triethanolamine; 1-4 parts coupling agent; 1-5 parts wetting agent; and 600-850 parts water. The water-resistant soil stabilizer of the present invention can improve soil density, has a good effect on solidifying heavy metals in soil, enhance soil compressive strength, and give the soil good water stability and good water resistance.

Description

Technical Field

[0001] This invention relates to the fields of solid waste resource utilization and soil solidification technology, specifically to a water-resistant soil solidification agent and its preparation and application methods. Background Technology

[0002] Soil stabilizer, short for soil stabilizing admixture, is a new type of energy-saving and environmentally friendly engineering material synthesized from various inorganic and organic materials to stabilize various types of soil. For soils requiring reinforcement, based on the soil's physical and chemical properties, only a certain amount of stabilizer needs to be added, mixed thoroughly, and compacted to achieve the required performance indicators.

[0003] Soil stabilizers have a wide range of applications, including building foundations, dam slope protection, tidal flat silt, dust control and sand fixation, and industrial sludge solidification. They can not only achieve reinforcement and strengthening effects, but also effectively stabilize pollutants and prevent them from seeping into and polluting the environment.

[0004] Soil stabilizers can be classified into powder and liquid forms, and into three main categories based on their composition: inorganic, organic, and bio-enzyme-based. Inorganic soil stabilizers are mainly powder-based, including lime-cement and slag-silicate stabilizers. They offer good stability and low cost but are prone to cracking and have insufficient early strength. Organic soil stabilizers are liquid polymers with high molecular weight; they require small amounts and have good water resistance, but their application is limited and they are prone to aging. Bio-enzyme-based stabilizers are biological stabilizers, effective for stabilizing highly plastic clays, but they are expensive to prepare and easily degrade, affecting their lifespan. Most known stabilizers currently have insufficient water resistance, and the water stability of applied soil stabilizers is inadequate, especially liquid stabilizers which fail to solidify the foundation soil after prolonged rainwater immersion.

[0005] Considering comprehensive performance, while seeking high strength performance in soil conditioners, high water resistance is a crucial indicator for maintaining strength and ensuring durability. Achieving satisfactory results in terms of strength, water resistance, and economic efficiency (including material cost, waste utilization, and ease of construction) from inexpensive and renewable raw materials such as biomass is an urgent task in the development of soil conditioners. For applications requiring high strength and durability, such as road and riverbank engineering, organic (especially biomass-based) inorganic composite conditioners offer advantages.

[0006] Organosilicon is a diverse class of new chemical products with excellent performance and wide applications, often referred to as "industrial MSG." Various silanes and siloxane intermediates, as well as silicone oils, silicone rubbers, silicone resins (including their secondary processed products), coupling agents, and other products derived from them, have been widely used and played a positive role in industries such as electronics, construction, automotive, textiles, light industry, cosmetics, medical, and food. Practical experience has proven that organosilicon emulsions have excellent water resistance; incorporating a small amount of organosilicon emulsion can significantly improve soil water stability.

[0007] Phosphogypsum is an industrial solid waste produced by the wet process of phosphoric acid production. It contains certain organic and inorganic phosphorus residues, making it acidic. Producing 1 ton of phosphoric acid generates approximately 4-5 tons of phosphogypsum. Currently, my country has approximately 600 million tons of phosphogypsum stockpiled, and stockpiles are nearing saturation. However, the utilization rate of bulk solid wastes such as phosphogypsum and phosphate slag is less than 10%. This large stockpile and low consumption rate result in a significant waste of land resources, threatening environmental safety and easily triggering landslides, mudslides, and other safety accidents, causing serious casualties and property damage. If not properly managed, phosphorus, sulfur, and heavy metals in phosphogypsum can seep out of stockpiles with rainwater, causing pollution to surrounding soil, groundwater, and rivers. The low activity and slow hydration of undisturbed phosphogypsum limit its resource utilization pathways. This situation can be improved through activation; currently, the main activation methods include physical activation, thermal activation, and chemical activation. Physical activation involves using mechanical methods to improve the fineness of phosphogypsum, thereby enhancing its activity. Thermal activation involves providing heat to phosphogypsum to increase its activity. Chemical activation involves introducing a small amount of activator to participate in and accelerate the hydration reaction of phosphogypsum materials under alkaline conditions. Current applications of phosphogypsum include: as a raw material for cement, sulfuric acid, and building gypsum; as a retarder; and in the preparation of cementitious materials with other industrial wastes. However, these applications suffer from low consumption rates and problems such as high cost and poor water resistance. Summary of the Invention

[0008] The purpose of this invention is to overcome the above-mentioned shortcomings of the prior art and to provide a water-resistant soil stabilizer, its preparation method, and its application method.

[0009] To achieve the above-mentioned objective, in a first aspect, the present invention provides a water-resistant soil stabilizer, comprising component A and component B, wherein component A and component B each comprise the following raw materials in parts by weight:

[0010] Component A comprises the following raw materials in parts by weight: 500-700 parts phosphogypsum; 1-5 parts coke powder; 80-160 parts fly ash; 10-20 parts calcium aluminate; 50-100 parts silicate cement clinker; 100-200 parts steel slag powder; 100-200 parts mineral powder; 5-10 parts quicklime; 5-10 parts sodium sulfate; 2-8 parts calcined alunite; and 1-5 parts readily soluble solid water glass.

[0011] 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 adduct; 5-12 parts of zinc acetate; 1-5 parts of zirconium hydroxide; 1-5 parts of triethanolamine; 1-4 parts of coupling agent; 1-5 parts of wetting agent; and 600-850 parts of water.

[0012] In one embodiment, the phosphogypsum comprises CaSO4•2H2O, P2O5, MgO, Fe2O3, Al2O3, and CaO.

[0013] The coke powder is finely ground metallurgical coking coal with a carbon content >90% and a fineness of 280 mesh to 400 mesh.

[0014] The specific surface area of ​​the steel slag powder is 400-800 m². 2 / kg, with a mesh size of 380-600 mesh, and its components include Al2O3, SiO2, CaO, Fe2O3, SO3, C4A3, C2S and C4AF;

[0015] The mineral powder contains 50% to 60% iron oxide and 30% to 40% silicon oxide.

[0016] The composition of the fast-dissolving solid water glass includes 2.5% to 3.8% fast-dissolving solid sodium silicate.

[0017] In one embodiment, the hydroxyl silicone oil emulsion has a molar mass of 30-60 g / mol and a pH value of 5.5-7.

[0018] The viscosity of the methyl hydrogen silicone oil emulsion is <50 mm. 2 / s, pH value 3-4, hydrogen mass fraction 1-1.5%;

[0019] The zinc acetate is zinc acetate dihydrate, containing two molecules of water of crystallization;

[0020] The zirconium hydroxide is of industrial grade and contains 8 molecules of water of crystallization.

[0021] The wetting agent is organosilicon;

[0022] The water is deionized water.

[0023] Secondly, the present invention provides a method for preparing a water-resistant soil stabilizer, comprising:

[0024] Step 1: The raw phosphogypsum is subjected to flotation to remove impurities, solid-liquid separation and drying to obtain phosphogypsum after impurity removal;

[0025] Step 2: Thoroughly mix the phosphogypsum after impurity removal with coke powder, sodium sulfate and calcined alunite to obtain the first mixture;

[0026] Step 3: Irradiate the first mixture using a microwave generator to obtain the first mixture after microwave irradiation;

[0027] Step 4: Mix the microwave-irradiated first mixture with silicate cement clinker, steel slag powder, mineral powder, and fly ash in a certain proportion and then send it to an ultrafine pulverizer for pulverization to obtain the second mixture;

[0028] Step 5: Mix and grind the second mixture with calcium aluminate, quicklime, and fast-dissolving solid water glass to obtain component A;

[0029] Step 6: Add hydroxyl silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolamine, coupling agent, and wetting agent to water in sequence, and stir continuously at room temperature to dissolve them, thereby obtaining component B.

[0030] In one embodiment, in step three, the first mixture is irradiated at 145°C for 20 to 40 minutes using a microwave generator of 300 MHz to 945 MHz to obtain the first mixture after microwave irradiation.

[0031] In one embodiment, in step four, the microwave-irradiated first mixture is mixed with silicate cement clinker, steel slag powder, mineral powder, and fly ash in a certain proportion and then sent to an ultrafine pulverizer to be pulverized to 380-480 mesh to obtain the second mixture.

[0032] In step six, hydroxyl silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolamine, coupling agent, and wetting agent are added to water in sequence. The mixture is stirred continuously at 100-200 r / min at room temperature until dissolved, and then stirred for 30 minutes to obtain component B.

[0033] Thirdly, this invention provides an application of a water-resistant soil stabilizer in hydraulic slope protection, tidal flat stabilization, road base and subbase, grouting materials, and the built environment.

[0034] Fourthly, the present invention provides a method for using a water-resistant soil stabilizer, comprising:

[0035] The A component is first mixed with the solidified material, and then the B component and water are added for a second mixing to obtain a mixture. The mixture is then filled or compacted and cured to obtain solidified soil.

[0036] In one embodiment, the weight ratio of component A of the water-resistant soil stabilizer to the solidified material is 1:9 to 3:7, and the amount of component B of the water-resistant soil stabilizer is 2 to 10% of the weight of the solidified material; in the step of adding component B and water for a second mixing after mixing, the amount of water is 7 to 55% of the weight of the solidified material.

[0037] In one embodiment, the first mixing time is 2-3 minutes, and the second mixing time is 3-5 minutes.

[0038] The advantages and beneficial effects of this invention compared to the prior art are as follows:

[0039] (1) In this invention, phosphogypsum is a complex crystalline substance with multiple components. The preparation method provided by this invention uses a microwave-physical-chemical composite excitation method to excite the soluble P2O5 and Fe in phosphogypsum. 2+ The process involves stabilizing the material by reducing its harmful components to crystals, transforming them into harmless, stable materials, and then encapsulating them with a gelling agent.

[0040] (2) When irradiated with microwaves, 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, this will generate thermal stress between the minerals, which will promote the formation of cracks at the interface between the minerals. At the same time, it will effectively promote the dissociation of monomers in the microwave-absorbing minerals and increase the effective reaction area of ​​the microwave-absorbing minerals. On the other hand, the heating process will cause phosphogypsum to dehydrate and undergo crystal transformation, phase transformation, or chemical reaction.

[0041] (3) In this invention, the organosilicon component B reacts together with component A and forms an organosilicon film on the surface of the solidified soil. This not only effectively improves the solidification performance of the soil solidifier, but also effectively improves the water resistance of the solidified soil, extends the service life, reduces social costs, saves resources, and improves the efficiency of soil solidification. It is suitable for soil solidification treatment of roads, airports and farmland slopes that are subject to natural rainwater erosion. Detailed Implementation

[0042] To make the technical problem to be solved, the technical solution, and the beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.

[0043] In a first aspect, the present invention provides a water-resistant soil stabilizer, comprising component A and component B, wherein component A and component B each comprise the following raw materials in parts by weight:

[0044] Component A comprises the following raw materials in parts by weight: 500-700 parts phosphogypsum; 1-5 parts coke powder; 80-160 parts fly ash; 10-20 parts calcium aluminate; 50-100 parts silicate cement clinker; 100-200 parts steel slag powder; 100-200 parts mineral powder; 5-10 parts quicklime; 5-10 parts sodium sulfate; 2-8 parts calcined alunite; and 1-5 parts readily soluble solid water glass.

[0045] 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 adduct; 5-12 parts of zinc acetate; 1-5 parts of zirconium hydroxide; 1-5 parts of triethanolamine; 1-4 parts of coupling agent; 1-5 parts of wetting agent; and 600-850 parts of water.

[0046] Furthermore, the phosphogypsum comprises CaSO4•2H2O, P2O5, MgO, Fe2O3, Al2O3, and CaO; the phosphogypsum is an ultrafine acidic waste produced by phosphate chemical industry, and its main components are CaSO4•2H2O, P2O5, MgO, Fe2O3, Al2O3, and CaO, which can provide calcium ions and sulfate ions for soil stabilizers;

[0047] The coke powder is finely ground metallurgical coking coal with a carbon content >90%, with a fineness of 280 mesh to 400 mesh, and is used as a microwave absorbing heating material.

[0048] The fly ash mentioned above is the fine ash collected from the flue gas after coal combustion in power plants. Fly ash is the main solid waste discharged by coal-fired power plants, has a pozzolanic effect, and is a major component in the formation of hydrated calcium silicate.

[0049] The calcium aluminate mentioned is commercially available high-alumina cement, whose main chemical components are Al2O3 and CaO. It has strong activity and provides an aluminum source for cementitious materials.

[0050] The silicate cement clinker is an unprocessed and finely ground finished product produced by a cement plant, which provides active activating substances for cementitious materials;

[0051] The steel slag powder is steel slag that has been finely ground from waste slag produced during steelmaking in steel plants after hot quenching, and the specific surface area of ​​the steel slag powder is 400-800 m². 2 / kg, with a mesh size of 380-600 mesh, and its components include Al2O3, SiO2, CaO, Fe2O3, SO3, C4A3, C2S and C4AF, etc.;

[0052] The ore powder mentioned is blast furnace slag, a waste product generated during the ironmaking process, whose main components are iron oxide and silicon oxide. The iron oxide content is 50%–60%, and the silicon oxide content is 30%–40%. In addition, the slag also contains small amounts of impurities such as aluminum oxide, calcium oxide, and magnesium oxide. After being ground to a finer mesh (above 400 mesh), the finely ground slag contains more than 30% active calcium, silicon, aluminum, and other inorganic substances, with an activity index greater than 95%. Silicon oxide in the blast furnace slag is an active inorganic compound that provides the system with active silicon exhibiting a pozzolanic effect.

[0053] The quicklime used is commercially available CaO. As an alkaline activator, the addition of quicklime can adjust the alkalinity of the anhydrous gypsum slurry and activate the activity of the slag. In the anhydrous gypsum slurry after the addition of quicklime, the lime first reacts with water and rapidly hydrates to form Ca(OH)2, creating an alkaline medium environment for the entire system. Only then does dihydrate gypsum form. The presence of the alkaline medium activates the potential activity of the slag, generating ettringite crystals and hydrated calcium silicate gels, which have higher strength and stability than dihydrate gypsum and lower solubility in water. These newly added products continuously fill and encapsulate the structure of dihydrate gypsum and anhydrous gypsum, making the overall structure more compact and thus improving early and later strength.

[0054] The sodium sulfate used is commercially available sodium sulfate (Na₂SO₄). The addition of sodium sulfate can accelerate the formation of supersaturation in anhydrous gypsum and reduce its crystallization activation energy, thus accelerating crystallization and significantly improving the hydration rate. Therefore, the addition of sodium sulfate can significantly improve the early strength of hardened anhydrous gypsum.

[0055] The calcined alunite is commercially available and is a natural mineral mainly composed of potassium aluminum sulfate double salt. It is produced by calcination, and the required effective component is aluminum oxide. The higher the sulfur trioxide content, the better its water activation properties. Under the activation of alkali-sulfate, alunite forms ettringite, which improves the strength of cement stone. After calcination, dehydration, and activation, alunite has high solubility and the ability to react with cement hydrates. It can quickly interact with gypsum to generate ettringite, thereby further accelerating and deepening the hydration and hardening of cement.

[0056] The main component of the fast-dissolving solid water glass is 2.5% to 3.8% fast-dissolving solid sodium silicate; it is an early-strength alkaline activator in the system. The role of water glass is to react with anhydrous gypsum particles to precipitate Ca(OH)2, making the anhydrous gypsum slurry alkaline, which can increase the solubility of anhydrous gypsum and generate more dihydrate gypsum, thus having a significant activating effect on accelerating the hydration of anhydrous gypsum.

[0057] Furthermore, the hydroxyl silicone oil emulsion (hydroxyl emulsion) has a molar mass of 30~60 g / mol and a pH value of 5.5~7. It is an emulsion polymer and is the main component for forming the organosilicon film.

[0058] The methyl hydrogen-containing silicone oil emulsion (hydrogen emulsion) has a viscosity of <50 mm2 / s, a pH value of 3-4, and a hydrogen mass fraction of 1-1.5%. It is a mechanical emulsifier and can form an organosilicon film crosslinking agent.

[0059] The epoxy polyamine adduct is an industrial product. The synthesis method is to add an excess of amine to a single-component epoxy synthesis system. It can act as an emulsion stabilizer and increase the adhesion of organosilicon films.

[0060] The zinc acetate is zinc acetate dihydrate, containing two molecules of water of crystallization, and is tertiary, serving as a hydrolysis condensation catalyst and filler.

[0061] The zirconium hydroxide is of industrial grade and contains 8 molecules of water of crystallization. It is deposited in soil gaps, promotes the directional arrangement of silicon-oxygen bonds, and increases the waterproof effect.

[0062] The triethanolamine acts as a hydrolysis-condensation catalyst.

[0063] The coupling agent, brand name KH560, can increase the compatibility of the components.

[0064] The wetting agent is organosilicon H140, which can improve the wetting and dispersibility of the material and has a water-reducing effect;

[0065] The water is deionized water, used as a diluent for component B.

[0066] Secondly, the present invention provides a method for preparing a water-resistant soil stabilizer, comprising:

[0067] Step 1: The phosphogypsum is subjected to flotation to remove impurities, solid-liquid separation and drying to obtain the phosphogypsum after impurity removal;

[0068] Step 2: Thoroughly mix the phosphogypsum after impurity removal with coke powder, sodium sulfate and calcined alunite to obtain the first mixture;

[0069] Step 3: Irradiate the first mixture using a microwave generator to obtain the first mixture after microwave irradiation;

[0070] Step 4: Mix the microwave-irradiated first mixture with silicate cement clinker, steel slag powder, mineral powder, and fly ash in a certain proportion and then send it to an ultrafine pulverizer for pulverization to obtain the second mixture;

[0071] Step 5: Mix and grind the second mixture with calcium aluminate, quicklime, and fast-dissolving solid water glass to obtain component A;

[0072] Step 6: Add hydroxyl silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolamine, coupling agent, and wetting agent to water in sequence. Stir continuously at 100-200 r / min at room temperature until dissolved, and continue stirring for 30 minutes to obtain component B.

[0073] Furthermore, in step three, the first mixture is irradiated at 145°C for 20 to 40 minutes using a microwave generator with a frequency of 300 MHz to 945 MHz to obtain the first mixture after microwave irradiation.

[0074] Furthermore, in step four, the microwave-irradiated first mixture is mixed with silicate cement clinker, steel slag powder, mineral powder, and fly ash in a certain proportion and then sent to an ultrafine pulverizer to be pulverized to 380-480 mesh to obtain the second mixture.

[0075] In step six, hydroxyl silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolamine, coupling agent, and wetting agent are added to water in sequence. The mixture is stirred continuously at 100-200 r / min at room temperature until dissolved, and then stirred for 30 minutes to obtain component B.

[0076] Microwave irradiation stimulates mineral activity, causing internal vibrations and heat generation. This promotes crack formation at the mineral interfaces, increasing the specific surface area of ​​the minerals and facilitating adsorption, bonding, and reaction with soil particles, thereby enhancing soil stabilization. Microwave irradiation can also dehydrate phosphogypsum, causing crystal transformation and phase transition reactions, converting it into large quantities of hemihydrate and anhydrous gypsum, further improving its soil stabilization effect.

[0077] Thirdly, this invention provides the application of water-resistant soil stabilizers in hydraulic slope protection, tidal flat stabilization, road base and subbase, grouting materials, and the built environment.

[0078] The aforementioned water-resistant soil stabilizer is applicable to applications in fields such as water conservancy slope protection, tidal flat stabilization, road base and subbase, grouting materials, and building environment. It features simple construction, excellent performance, low cost, and environmental friendliness.

[0079] Fourthly, the present invention provides a method for using a water-resistant soil stabilizer, comprising:

[0080] Step 1: Mix component A with the solidified material for the first time, then add component B and water for the second mixing to obtain a mixture;

[0081] Step one is as follows: First, mix component A with the solidified material for 2-3 minutes, then add component B and an appropriate amount of water for a second mixing, and mix for 3-5 minutes to obtain a mixture.

[0082] Step 2: Fill or compact the mixture, and then cure it to obtain solidified soil.

[0083] Step two is as follows: When used for sand and soil solidification, the mixture is poured into a 7.07 cm*7.07 cm*7.07 cm mold and vibrated to compact. After 24 hours, the mold is removed, and the mixture is cured in a standard curing box for 28 days. The strength is then tested using a compressive strength testing machine. Or, when used for road base and subbase, the mixture is filled into a cylindrical steel mold, compacted using a press, and after demolding, sealed with plastic wrap and placed in a standard curing box for 7 days. The unconfined compressive strength is then tested using a compressive strength testing machine after 7 days.

[0084] Furthermore, in step one, the weight ratio of component A of the water-resistant soil stabilizer to the solidified object is 1:9 to 3:7, and the amount of component B of the water-resistant soil stabilizer is 2 to 10% of the weight of the solidified object; in the step of adding component B and water for a second mixing after mixing, the amount of water is 7 to 55% of the weight of the solidified object.

[0085] The positive effects of controlling the dosage of components A and 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 increase the curing cost to a certain extent, and waste resources if it seriously exceeds the strength index requirements; if the content of the water-resistant soil curing agent is too low, it will fail to meet the curing strength index requirements to a certain extent. Specifically, the weight ratio of component A to the cured material is 1:9 to 3:7, for example, 1:9, 15:85, 2:8, 25:75, 3:7, etc., and the dosage of component B is 2% to 10% of the weight of the cured material, for example, 2%, 4%, 6%, 8%, 10%.

[0086] The positive effects of controlling water usage: Within this range, the moisture content is determined based on the fluidity index of the mixture during construction. If the water content is too high, it will prolong the setting time of the solidified soil and reduce its compressive strength; if the water content is too low, it will result in incomplete hydration of the soil stabilizer, reducing the solidification effect. Specifically, the water usage is 7-55% of the weight of the material being solidified, for example, 7%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, and 55%.

[0087] This invention has undergone numerous experiments, and some of the experimental results are presented here for reference to further describe the invention in detail. The following is a detailed description in conjunction with specific embodiments.

[0088] Example 1

[0089] By weight, 800 parts of phosphogypsum, 4 parts of coke powder, 10 parts of sodium sulfate, and 8 parts of calcined alum stone were thoroughly stirred at 75 r / min for 5 min. The mixture was then irradiated at 145℃ for 20–40 min using a 5.0 kW, 945 MHz microwave generator. The mixture was then mixed with 50 parts of silicate silicate cement clinker, 100 parts of steel slag powder, 100 parts of mineral powder, and 150 parts of fly ash. The mixture was pulverized to 380–400 mesh and then mixed with 20 parts of calcium aluminate, 10 parts of quicklime, and 5 parts of fast-dissolving solid water glass and ground to obtain component A.

[0090] By weight, 70 parts of hydroxyl silicone oil emulsion (hydroxyl 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 triethanolamine, 3 parts of coupling agent, and 5 parts of wetting agent were added to 800 parts of water. The mixture was stirred continuously at 100 r / min at room temperature for 30 minutes to dissolve the emulsion and obtain component B.

[0091] Example 2

[0092] By weight, 600 parts of phosphogypsum, 2 parts of coke powder, 8 parts of sodium sulfate, and 6 parts of calcined alum stone were thoroughly stirred at 75 r / min for 5 min. The mixture was then irradiated at 145℃ for 20–40 min using a 5.0 kW, 945 MHz microwave generator. The mixture was then mixed with 60 parts of silicate silicate cement clinker, 150 parts of steel slag powder, 150 parts of mineral powder, and 100 parts of fly ash. The mixture was pulverized to 380–400 mesh and then mixed with 16 parts of calcium aluminate, 8 parts of quicklime, and 4 parts of fast-dissolving solid water glass and ground to obtain component A.

[0093] By weight, 70 parts of hydroxyl silicone oil emulsion (hydroxyl 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 triethanolamine, 3 parts of coupling agent, and 5 parts of wetting agent were added to 800 parts of water. The mixture was stirred continuously at 100 r / min at room temperature for 30 minutes to dissolve the emulsion and obtain component B.

[0094] Example 3

[0095] By weight, 500 parts of phosphogypsum, 2 parts of coke powder, 6 parts of sodium sulfate, and 4 parts of calcined alum stone were thoroughly stirred at 75 r / min for 5 min. The mixture was then irradiated at 145℃ for 20–40 min using a 5.0 kW, 945 MHz microwave generator. The mixture was then mixed with 80 parts of silicate silicate cement clinker, 200 parts of steel slag powder, 200 parts of mineral powder, and 100 parts of fly ash. The mixture was pulverized to 380–400 mesh and then mixed with 12 parts of calcium aluminate, 6 parts of quicklime, and 2 parts of fast-dissolving solid water glass and ground to obtain component A.

[0096] By weight, 70 parts of hydroxyl silicone oil emulsion (hydroxyl 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 triethanolamine, 3 parts of coupling agent, and 5 parts of wetting agent were added to 800 parts of water. The mixture was stirred continuously at 100 r / min at room temperature for 30 minutes to dissolve the emulsion and obtain component B.

[0097] Application Example 1-11

[0098] According to Table 1, the water-resistant soil stabilizers obtained in Examples 1-3 were mixed with red clay at different weight ratios and different water-to-material ratios to form specimens. The specimens were then soaked in water on the last day of the curing period. Dry-hardened water-stabilized specimens and fluidized stabilized soil specimens were formed according to different water-to-material ratios. The specific steps are as follows:

[0099] The A component of the water-resistant soil stabilizer obtained in Examples 1-3 was first mixed with red clay. After mixing, the B component and water were added for a second mixing to obtain a mixture. This mixture was then filled or compacted, cured, and soaked in water on the last day of the curing period. This process is used as Application Examples 1-9. Dry-hardened water-stabilized specimens and fluidized solidified soil specimens were formed according to different water-to-material ratios. The water-to-material ratio refers to the ratio of the total weight of water to the total weight of the solid material. The "material" in the water-to-material ratio refers to the total weight of the A component of the water-resistant soil stabilizer and the red clay.

[0100] The B component from any one of Examples 1, 2, or 3 is mixed with red clay and water to obtain a mixture. The mixture is then filled or compacted, cured, and soaked in water on the last day of the curing period. This process is referred to 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. The material in the water-to-material ratio refers to the total weight of the A component of the water-resistant soil stabilizer and the red clay.

[0101] Cement and red clay are first mixed, and then mixed with water to obtain a mixture. The mixture is compacted, cured, and then soaked in water on the last day of the curing period. This process is described as Application Example 11. In the first mixture, the weight ratio of cement to red clay is 3:7. The water-to-material ratio refers to the ratio of the total weight of water to the total weight of solid materials. The "material" in the water-to-material ratio refers to the total weight of component A of the water-resistant soil stabilizer and the red clay.

[0102] Table 1. Application and usage of water-resistant soil stabilizers

[0103]

[0104] Table 2. Performance test results of water-resistant soil stabilizer applied to red clay.

[0105]

[0106] The performance test results of the water-resistant soil stabilizer applied to red clay are shown in Table 2. It can be seen that the water-resistant soil stabilizer provided in this application has a good stabilization effect, and the compressive strength of red clay after 28 days of immersion in water can reach 1-4 MPa. A comparison of the results of application examples 1 and 2, 3 and 4, and 5 and 6 shows that the stabilization effect of red clay improves with increasing dosage of component A of the water-resistant soil stabilizer. A comparison of the results of application examples 1-6 and 7-9 shows that fluidized solidified red clay has better compressive strength and water resistance than dry-hardened solidified red clay.

[0107] Application Example 12-15

[0108] According to Table 3, the A component obtained in Examples 1-3 was mixed with undisturbed phosphogypsum at a weight ratio of 3:7, and then 4% of the B component was added. Dry-hardened water-stabilized specimens were formed and subjected to unconfined compressive strength tests. The specimens were then immersed in water on the last day of the curing period. The specific steps are as follows:

[0109] The A component of the water-resistant soil stabilizer obtained in Examples 1-3 was mixed with undisturbed phosphogypsum at a weight ratio of 3:7. After mixing, the B component and water were added for a second mixing to obtain a mixture. The mixture was compacted and then cured. Dry-hardened water-stable specimens were formed and subjected to unconfined compressive strength tests. The specimens were then immersed in water on the last day of the curing period. This process is referred to 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. The material in the water-to-material ratio refers to the total weight of the A component of the water-resistant soil stabilizer and the undisturbed phosphogypsum.

[0110] Cement and undiluted phosphogypsum were first mixed, and then mixed with water to obtain a mixture. The mixture was compacted, cured, and then soaked in water on the last day of the curing period. This process is described in Application Example 15. In the first mixture, the weight ratio of cement to undiluted phosphogypsum was 3:7. The water-to-material ratio refers to the ratio of the weight of water to the total weight of the solid material. The "material" in the water-to-material ratio refers to the total weight of component A of the water-resistant soil stabilizer and the undiluted phosphogypsum.

[0111] Table 3. Application Methods of Water-Resistant Soil Stabilizer in Unrefined Phosphogypsum

[0112]

[0113] Table 4. Performance test results of water-resistant soil stabilizer applied to undisturbed phosphogypsum

[0114]

[0115] The performance test results of the water-resistant soil stabilizer applied to undisturbed phosphogypsum are shown in Table 4. It can be seen that the water-resistant soil stabilizer provided in this application has a good curing effect, and the compressive strength after 28 days of immersion in water on undisturbed phosphogypsum can reach 14-16 MPa. If applied to road base and subbase, it can meet the heavy traffic requirements of 3.0-5.0 MPa for Class II and lower highways. As can be seen from Application Examples 11 and 15, the water-resistant soil stabilizer provided by this invention has a similar application effect to cement. However, the water-resistant soil stabilizer provided in this invention is entirely prepared from industrial solid waste, which has the advantage of low cost and realizes the resource utilization of industrial solid waste, resulting in good environmental and social benefits.

[0116] The above description is merely 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 within the protection scope of the present invention.

Claims

1. A water-resistant soil stabilizer, characterized in that, It includes component A and component B, wherein component A and component B each comprise the following raw materials in parts by weight: Component A comprises the following raw materials in parts by weight: 500-700 parts phosphogypsum; 1-5 parts coke powder; 80-160 parts fly ash; 10-20 parts calcium aluminate; 50-100 parts silicate cement clinker; 100-200 parts steel slag powder; 100-200 parts mineral powder; 5-10 parts quicklime; 5-10 parts sodium sulfate; 2-8 parts calcined alunite; and 1-5 parts readily soluble solid water glass. 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 adduct; 5-12 parts of zinc acetate; 1-5 parts of zirconium hydroxide; 1-5 parts of triethanolamine; 1-4 parts of coupling agent; 1-5 parts of wetting agent; and 600-850 parts of water. The epoxy polyamine adduct is synthesized by adding an excess of amine to a single-component epoxy synthesis system. The water-resistant soil stabilizer is prepared by the following method: Step 1: The phosphogypsum is subjected to flotation to remove impurities, solid-liquid separation and drying to obtain the phosphogypsum after impurity removal; Step 2: Thoroughly mix the phosphogypsum after impurity removal with coke powder, sodium sulfate and calcined alunite to obtain the first mixture; Step 3: Irradiate the first mixture at 145°C for 20-40 minutes using a microwave generator with a frequency of 300 MHz to 945 MHz to obtain the first mixture after microwave irradiation. Step 4: Mix the microwave-irradiated first mixture with silicate cement clinker, steel slag powder, mineral powder, and fly ash in a certain proportion and then send it to an ultrafine pulverizer for pulverization to obtain the second mixture; Step 5: Mix and grind the second mixture with calcium aluminate, quicklime, and fast-dissolving solid water glass to obtain component A; Step 6: Add hydroxyl silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolamine, coupling agent, and wetting agent to water in sequence, and stir continuously at room temperature to dissolve them, thereby obtaining component B.

2. The water-resistant soil stabilizer according to claim 1, characterized in that: The components of the phosphogypsum include CaSO4•2H2O, P2O5, MgO, Fe2O3, Al2O3 and CaO; The coke powder is finely ground metallurgical coking coal with a carbon content >90% and a fineness of 280 mesh to 400 mesh. The specific surface area of ​​the steel slag powder is 400-800 m². 2 / kg, with a mesh size of 380-600 mesh, and its components include Al2O3, SiO2, CaO, Fe2O3, SO3, C4A3, C2S and C4AF; The mineral powder contains 50% to 60% iron oxide and 30% to 40% silicon oxide. The composition of the fast-dissolving solid water glass includes 2.5% to 3.8% fast-dissolving solid sodium silicate.

3. The water-resistant soil stabilizer according to claim 1, characterized in that: The viscosity of the methyl hydrogen silicone oil emulsion is <50 mm. 2 / s, pH value 3-4, hydrogen mass fraction 1-1.5%; The zinc acetate is zinc acetate dihydrate, containing two molecules of water of crystallization; The zirconium hydroxide is of industrial grade and contains 8 molecules of water of crystallization. The wetting agent is organosilicon; The water is deionized water.

4. The water-resistant soil stabilizer according to claim 1, characterized in that, In step four, the microwave-irradiated first mixture is mixed with silicate cement clinker, steel slag powder, mineral powder, and fly ash in a certain proportion and then sent to an ultrafine pulverizer to be pulverized to 380-480 mesh to obtain the second mixture. In step six, hydroxyl silicone oil emulsion, methyl hydrogen silicone oil emulsion, epoxy polyamine adduct, zinc acetate, zirconium hydroxide, triethanolamine, coupling agent, and wetting agent are added to water in sequence. The mixture is stirred continuously at 100-200 r / min at room temperature until dissolved, and then stirred for 30 minutes to obtain component B.

5. The application of the water-resistant soil stabilizer according to claim 1, characterized in that, Applications in water conservancy slope protection, tidal flat solidification, road base and subbase, grouting materials and built environment.

6. The method of using the water-resistant soil stabilizer according to claim 1, characterized in that, include: The A component is first mixed with the solidified material, and then the B component and water are added for a second mixing to obtain a mixture. The mixture is then filled or compacted and cured to obtain solidified soil.

7. The method of use according to claim 6, characterized in that, The weight ratio of component A of the water-resistant soil stabilizer to the solidified material is 1:9 to 3:7, and the amount of component B of the water-resistant soil stabilizer is 2 to 10% of the weight of the solidified material; in the second mixing step of adding component B and water after mixing, the amount of water is 7 to 55% of the weight of the solidified material.

8. The method of use according to claim 7, characterized in that, The first mixing time is 2-3 minutes, and the second mixing time is 3-5 minutes.

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