Environment-friendly non-metallic base siliceous material and preparation method thereof

Abstract

This invention discloses an environmentally friendly non-metallic silicon-based material and its preparation method. By weight, the material comprises 80-92 parts of aluminosilicate solid waste raw material, 5-10 parts of nano-sized magnesium aluminum spinel, 1.5-3.8 parts of a composite rare earth polymorphic modifier, 0.4-1.2 parts of a surface energy gradient regulator, 0.6-1.8 parts of a vapor deposition epitaxial precursor, and 0.2-0.5 parts of a kinetic auxiliary stabilizer. This invention induces rare earth ions to enter the crystal lattice through a high-temperature melting infiltration process, thereby strengthening the thermal stress framework; utilizes supersonic mechanical chemical activation technology to construct an amorphous high-energy active defect layer of 150-350 nm on the powder surface; and employs plasma-enhanced vapor deposition epitaxy to grow a composite heterogeneous shell of 40-100 nm, ultimately achieving energy gradient balance through molecular grafting. This material possesses high density, strong hydrophobicity, and self-leveling properties, effectively solving the technical challenges of low activity, easy moisture absorption, and poor thermal stability in solid waste. It is widely applicable to environmentally friendly fireworks, ultra-high strength concrete, and metallurgical refractory materials.

Description

Technical Field

[0001] This invention discloses an environmentally friendly non-metallic silicon-based material and its preparation method, belonging to the field of solid waste resource recycling technology. Background Technology

[0002] With the continuous advancement of global industrialization, the disposal and resource utilization of industrial solid waste has become a key factor restricting the development of a circular economy. Among the numerous industrial wastes, aluminosilicate solid wastes such as blast furnace slag, steel slag, perlite tailings, fly ash, and carbide slag are characterized by large quantities, wide distribution, large land occupation, and high environmental risks. The main chemical components of these solid wastes are mainly silicon dioxide and alumina. Although theoretically they have extremely high potential for resource recycling, in actual conversion processes, due to their inherent physical defects and chemical inertness, they have long been limited to road construction and landfill or low-density building material mixing, making it difficult to achieve high-value-added industrial applications. Existing utilization technologies typically use these solid wastes as inexpensive fillers, which not only fails to fully exploit the chemical potential energy of their microstructure but also introduces uncertainties to the mechanical properties and durability of the final product due to their large compositional fluctuations, high impurity content, and unstable surface energy. Especially under the policy background of "carbon peaking and carbon neutrality", how to transform these low-end aluminosilicate solid wastes into high-performance, environmentally friendly non-metallic silicon materials through refined modification technology has become a difficult problem that the new materials science and environmental engineering community is working together to solve.

[0003] From a microscopic perspective, untreated aluminosilicate solid waste often exhibits a highly polymerized inorganic network structure. Within these networks, silicon-oxygen tetrahedra and aluminum-oxygen tetrahedra are highly interlocked through shared oxygen atoms, forming a thermodynamically extremely stable lattice system. While this structure imparts a certain macroscopic hardness to the material, it also results in negligible chemical reactivity at room temperature and pressure. Traditional physical pulverization methods, although increasing specific surface area by reducing particle size, often have limited and diminishing returns due to the lack of activation of internal chemical bonds. Furthermore, simple mechanical pulverization easily generates numerous microcracks and irregular geometries on the particle surface. These defects often become sources of stress concentration in subsequent applications, such as in the formulation of ultra-high-strength concrete, leading to a decrease in the overall compressive and flexural strength of the material. Therefore, breaking this inherently stable chemical inertness at the lattice level and inducing metastable structures with specific reactivity potential is a primary prerequisite for advancing the high-end application of solid waste resource utilization.

[0004] Among existing modification attempts, chemical alkali activation technology has been widely discussed. This technology mainly induces the rupture of the aluminosilicate network through a strong alkaline environment, thereby releasing silica and alumina units with gelling activity. However, alkali activation technology has unavoidable drawbacks, such as poor workability due to excessively fast reaction rates, volume stability problems caused by subsequent alkali-aggregate reactions, and corrosion of equipment and secondary environmental pollution caused by strong alkaline environments. More importantly, traditional chemical modification often only focuses on improving the activity of particle surfaces, neglecting the energy conduction and continuity of particles at the microscopic level. When these modified powders are exposed to the natural environment, their highly active sites on the surface quickly adsorb water molecules from the air, forming a dense physical adsorption film. This not only makes the powders extremely prone to moisture absorption, agglomeration, clumping, and loss of flowability during storage and transportation, but also results in extremely poor interfacial compatibility when combined with organic polymers or metal matrices. This interfacial effect caused by surface energy imbalance directly limits the application of modified powders in precision manufacturing and high-end environmental protection industries.

[0005] In the fields of environmentally friendly fireworks and special materials, traditional reducing agents or fillers often rely on sulfur, magnesium aluminum powder, or natural non-metallic minerals. The combustion of sulfur releases large amounts of sulfur dioxide gas, a significant source of acid rain and smog. Although the industry has been exploring sulfur-free alternatives, existing fillers such as ordinary carbonaceous materials or low-activity silica powder often present safety hazards such as incomplete combustion, uncontrollable energy release rates, and high electrostatic sensitivity. Ordinary aluminosilicate solid waste, due to its high content of low-melting-point impurities and uneven crystalline phases, is prone to melting and slagging under instantaneous high temperatures, failing to provide a stable thermodynamic support system. This is mainly because traditional solid waste treatment processes lack precise control over lattice energy, making it impossible to construct a multiphase composite system at the microscopic level that can both participate in chemical reactions and maintain thermal stress balance.

[0006] Furthermore, for the metallurgical refractory materials industry, the resistance to slag erosion and thermal shock stability of aluminosilicate materials has always been a trade-off. In high-temperature molten salt environments, ordinary aluminosilicate materials, due to their high porosity and weak interfacial bonding, are extremely susceptible to penetration and erosion by molten metal and slag. Even if the erosion rate is slowed by increasing the material's density, the lack of an internal energy buffer mechanism during frequent thermal cycling often leads to large-scale spalling and cracking due to the accumulation of internal thermal stress. Currently, most high-end refractory materials on the market rely on expensive synthetic raw materials such as pure electrofused mullite or spinel, which not only drives up industrial costs but also contradicts the current global development strategy of energy conservation and resource recycling. This situation highlights the urgency of developing a siliceous material that can convert inexpensive solid waste in situ into high-performance, self-healing, or erosion-resistant materials.

[0007] Traditional powder coating techniques often employ physical coatings of silicone or stearic acid to address moisture absorption and agglomeration issues. However, this physical coating exhibits extremely poor bonding strength when subjected to supersonic gas flow stripping or high-temperature scorching. Organic coatings are not only easily lost during friction, but due to the significant polarity difference between them and the inorganic matrix, they often form distinct phase interfaces within the material. This broken energy gradient makes particles more prone to interfacial slippage under stress. In recent years, although some research has attempted to construct protective films on powder surfaces using vapor deposition technology, achieving atomic-level continuous growth of vapor precursors on ultrafine powders with extremely high specific surface areas, and establishing chemical bonding and anchoring between the heterogeneous shell and the particle matrix, remains a significant challenge in the global new materials field.

[0008] In the field of high-performance concrete, as building structures develop towards ultra-high, large-span, and extreme environments, higher demands are placed on the control of early-age strength and microstructure of the interfacial transition zone of cement-based materials. While traditional mineral powders or fly ash can improve later-age strength to some extent after incorporation, their early-age activity is low, and their effect on adjusting the water-cement ratio is limited. This is especially true when concrete strength reaches... At this stage, the width and density of the interface transition zone become bottlenecks limiting strength. Due to the uneven charge distribution on the surface of solid waste powder, it is difficult for it to achieve true molecular-level dispersion in cement paste, often forming tiny clusters of agglomerates. These agglomerates not only occupy valuable hydration space but also trap unreacted water, leading to increased porosity and a significant decrease in durability after concrete hardening. This further proves that existing simple crushing and physical mixing processes can no longer meet the needs of high-end industries.

[0009] To address the aforementioned technical challenges, researchers in this field have been exploring how to incorporate core-shell structure theory, lattice distortion theory, and low-temperature plasma technology into the treatment of inorganic solid waste. However, logically integrating these complex physicochemical reactions within a continuous industrial production process remains a significant challenge. For example, how to ensure the effective penetration of rare earth ions into the crystal lattice without losing expensive trace elements, how to capture and stabilize high-energy free radicals through kinetic means during supersonic fragmentation, and how to regulate surface energy modulators with different properties to achieve a balanced distribution of energy gradients—the intersection and complexity of these problems determine the profound scientific significance and application value of developing a novel environmentally friendly non-metallic silicon-based material and its preparation method.

[0010] In summary, existing aluminosilicate solid waste processing technologies generally suffer from common problems such as low modification levels, limited product functionality, low added value, and poor environmental adaptability. Especially when facing the safety and stability requirements of environmentally friendly fireworks, the interfacial compatibility required for high-strength concrete, and the high-temperature corrosion resistance required by the metallurgical industry, existing technical solutions often fall short. Therefore, developing a silicate material that deeply reconstructs the microstructure, constructs a topological core-shell structure, and achieves precise surface energy control can not only greatly broaden the application boundaries of solid wastes such as blast furnace slag and tailings, but also provide a new, internationally competitive production paradigm for the non-metallic mineral processing industry. This is of great significance for promoting the construction of a resource-saving and environmentally friendly society. This invention was developed against this backdrop, aiming to break through the bottlenecks in solid waste utilization through a synergistic and enhanced process, achieving a qualitative leap from waste to high-end functional materials. Summary of the Invention

[0011] This invention aims to address the technical challenges in the existing resource utilization of aluminosilicate solid waste, such as insufficient activation, easy moisture absorption and agglomeration, poor high-temperature stability, and limited application scope due to surface energy imbalance. It provides an environmentally friendly non-metallic silica-based material and its preparation method. This invention achieves the transformation of industrial solid waste from low-end fillers to high-end micro / nano functional materials through micro-lattice reconstruction, core-shell structure construction, and surface energy gradient regulation. It resolves the contradiction between flowability and stability in long-distance gas-jet transport, ultra-high-strength concrete applications, and environmentally friendly fireworks manufacturing. To achieve the objectives of this invention, the technical solution adopted is as follows: An environmentally friendly non-metallic silicon-based material, by weight, comprises the following components: 80-92 parts of aluminosilicate solid waste raw material, 5-10 parts of nano-sized magnesium aluminum spinel, 1.5-3.8 parts of composite rare earth polymorphic modifier, 0.4-1.2 parts of surface energy gradient regulator, 0.6-1.8 parts of vapor deposition epitaxial precursor, and 0.2-0.5 parts of kinetic auxiliary stabilizer.

[0012] According to an environmentally friendly non-metallic silicon-based material, the composite rare earth polymorphic modifier is composed of lanthanum oxide, neodymium oxide, praseodymium oxide and yttrium oxide mixed in a molar ratio of 5:3:2:1, and is prepared as a nitrate complex aqueous solution with a mass fraction of 15%~25%.

[0013] According to an environmentally friendly non-metallic silicon-based material, the vapor deposition epitaxial precursor is one or more of tetraethyl orthosilicate, hexamethyldisiloxane, and tritert-butoxyaluminum.

[0014] According to an environmentally friendly non-metallic silica-based material, the silicate solid waste raw material is one or more of blast furnace slag, steel slag, perlite tailings, fly ash or carbide slag.

[0015] According to an environmentally friendly non-metallic silicon-based material, the surface energy gradient modifier is one or more of pentafluorophenyltriethoxysilane, amino-modified polysiloxane, hyperbranched polyester, polyether-modified silicone oil, perfluoroalkyl polyether, and methyl oleate.

[0016] According to an environmentally friendly non-metallic silicon-based material, the kinetic auxiliary stabilizer is one or more of the following: carboxyl-terminated liquid nitrile rubber, modified polyvinyl alcohol, dimethyl carbonate, and epoxidized soybean oil extract.

[0017] A method for preparing an environmentally friendly non-metallic siliceous material, wherein the preparation process of the siliceous material includes the following specific steps: S1 crushes aluminosilicate solid waste to an average particle size of 0.1-2 mm, then sprays a complexing solution composed of composite rare earth polymorphic modifiers in stages. It is then fed into a reducing atmosphere rotary kiln with gradient temperature control for high-temperature melting and infiltration treatment at 1680-1760℃ for 3-6 hours; utilizing rare earth ions La... 3+ 、Nd 3+ Lattice substitution with the aluminosilicate framework in aluminosilicates induces lattice distortion and forms an interstitial solid solution with high thermal stability, thereby strengthening the thermal stress-bearing framework of the material at the microscopic level. S2 synergistically injects the prepared skeleton material with nano-sized magnesium aluminum spinel and kinetic auxiliary stabilizer into a supersonic airflow pulverization system. The airflow pressure is kept constant at 0.9~1.3MPa and the flow velocity is controlled at 450~650 m / s. Utilizing the intense shear force and shock wave generated by the material in the supersonic collision, an amorphous high-energy active defect layer with a depth of 150~350nm is induced on the powder surface, and a multi-level gradient particle size distribution is simultaneously achieved, with the median diameter controlled at 1.5~4.5μm. S3 transfers the prepared active powder into a plasma-enhanced vapor deposition chamber, introduces a vapor deposition epitaxial precursor with nitrogen as the carrier gas, and induces highly active secondary nucleation sites on the powder surface in a plasma field with a frequency of 13.56~13.66MHz and a power of 400~800 W. Then, an epitaxial shell layer of SiO2 and rare earth oxide composite with a thickness of 40~100nm is grown to form a core-shell structured modified aluminosilicate composite powder intermediate. S4 feeds the prepared intermediate into a fluidized bed mixer, adds a surface energy gradient modifier, and uses a high-speed mixing device at a speed of 4000~6000 rpm to branch the polysiloxane long links in the modifier to the hydroxyl sites of the heterogeneous shell, reducing the surface polarity of the particles and eliminating the surface energy gradient, ultimately obtaining a highly dense, strongly hydrophobic, and self-flowing siliceous material.

[0018] Compared with the prior art, the present invention has the following advantages: (1) Extremely high solid waste conversion capacity and excellent environmental benefits: This invention successfully realizes the high-value recycling and utilization of aluminosilicate solid waste, with the proportion of solid waste as basic raw material reaching 80-92%. Through lattice reconstruction of waste, it is transformed from a low-end, low-stability filler into a high-performance, self-healing silicon functional material. This not only significantly reduces the area of ​​industrial waste storage, but also enables nitrogen-free and sulfur-free production through plasma heteroepitaxial growth technology in the production process, possessing extremely high ecological and environmental value.

[0019] (2) Excellent particle flowability and zero-blockage gas jet transport characteristics: By introducing a surface energy gradient modifier and implementing molecular-level grafting, this invention completely eliminates the common surface energy abrupt changes in ultrafine powders. The energy levels on the powder surface exhibit a gradient distribution, significantly reducing the intermolecular forces and electrostatic attraction between particles. Experiments show that, without the addition of any chemical dispersant, the angle of repose of this material is reduced to below 25°. During long-distance, high-pressure gas jet transport, the particles exhibit fluid-like self-flowing characteristics, greatly reducing transport energy consumption and completely eliminating the common "pipe blockage" hazard in industrial production.

[0020] (3) Long-term stable "active freezing" ability and super hydrophobicity: This invention uniquely uses extraction kinetics to help stabilize the high-energy free radicals, and coordinates with in-situ growth using PECVD technology. The nano-heterogeneous shell creates an atomic-level barrier to isolate the internal active core. This gives the modified silica material superior hydrophobic properties and extremely low water absorption. Even after 12 months of storage in a humid environment, its chemical activity decay rate remains below 3%, overcoming the limitation of traditional active mineral powders that must be used "as soon as they are produced".

[0021] (4) Synergistic Enhancement of Multidimensional Mechanical Structure and Interface Anchoring Effect: When this invention is applied to ultra-high strength concrete, its core-shell particles can form a strong chemical bond with the cement matrix. The lattice distortion caused by rare earth doping can release huge secondary hydration potential energy during hydration, inducing the generation of a large amount of CSH gel. At the same time, nano-sized magnesium aluminum spinel acts as "interface pinning" points, effectively preventing the propagation of microcracks in the interface transition zone. Experiments have shown that the compressive strength of concrete incorporating this material can be significantly increased by 25-40%, and the flexural strength can be increased by more than 30%.

[0022] (5) Significantly Enhanced Thermal Stability and Dynamic Safety Protection: In the fields of environmentally friendly fireworks and metallurgy, this invention utilizes the synergistic effect of nano-scale magnesium-aluminum spinel and rare earth composite epitaxial shells to construct a microscopic "thermal trap" network. Under explosive mechanics or high-temperature erosion environments, this structure can rapidly absorb and disperse instantaneous impact energy, preventing local hotspot explosions. When applied in fireworks agents, the fluorinated / polarity balance layer on the particle surface can quickly dissipate the electrostatic charge generated by friction, reducing the mechanical sensitivity of the agent to an extremely low level, significantly improving the inherent safety of the production and ignition processes. Detailed Implementation

[0023] Example 1

[0024] After crushing the aluminosilicate solid waste raw material to an average particle size of 0.1 mm, it was sprayed with a complexing solution composed of composite rare earth polymorphic modifiers in stages, and then fed into a reducing atmosphere rotary kiln with gradient temperature control for high-temperature melting and infiltration treatment at 1680℃ for 3 hours; using rare earth ions La 3+ 、Nd 3+ Lattice substitution is performed with the aluminosilicate framework in aluminosilicates to induce lattice distortion and form an interstitial solid solution with high thermal stability, thereby strengthening the thermal stress-bearing framework of the material at the microscopic level. The prepared framework material is then synergistically injected into a supersonic airflow pulverization system with nano-sized magnesium aluminum spinel and a kinetic auxiliary stabilizer. The airflow pressure is kept constant at 0.9 MPa and the flow velocity is controlled at 450 m / s. Utilizing the intense shear force and shock wave generated by the material during supersonic collisions, a 150 nm deep lattice is induced on the powder surface. An amorphous high-energy active defect layer was formed, and a multi-level gradient particle size distribution was simultaneously achieved, with the median diameter controlled at 1.5 μm. The prepared active powder was transferred into a plasma-enhanced vapor deposition chamber, and nitrogen was used as the carrier gas to introduce the vapor deposition epitaxial precursor. In a plasma field with a frequency of 13.56 MHz and a power of 400 W, highly active secondary nucleation sites were induced on the powder surface, and a 40 nm thick SiO2 and rare earth oxide composite epitaxial shell was epitaxially grown to form a core-shell structured modified aluminosilicate composite powder intermediate. The prepared intermediate was fed into a fluidized bed mixer, and a surface energy gradient regulator was added. Using a high-speed mixing device at a speed of 4000 rpm, the polysiloxane long links in the regulator were branched to the hydroxyl sites of the heterogeneous shell, reducing the surface polarity of the particles and eliminating the surface energy gradient, finally obtaining a highly dense, strongly hydrophobic, and self-flowing siliceous material.

[0025] Example 2

[0026] After crushing the aluminosilicate solid waste raw material to an average particle size of 1 mm, it was sprayed with a complexing solution composed of composite rare earth polymorphic modifiers in stages, and then fed into a reducing atmosphere rotary kiln with gradient temperature control for high-temperature melting and infiltration treatment at 1720℃ for 4 hours; using rare earth ions La 3+ 、Nd 3+ Lattice substitution was performed with the aluminosilicate framework in aluminosilicates to induce lattice distortion and form an interstitial solid solution with high thermal stability, thereby strengthening the thermal stress-bearing framework of the material at the microscopic level. The prepared framework material was then synergistically injected into a supersonic airflow pulverization system with nano-sized magnesium aluminum spinel and a kinetic auxiliary stabilizer. The airflow pressure was kept constant at 1.1 MPa and the flow rate was controlled at 550 m / s. Utilizing the intense shear force and shock wave generated by the material during supersonic collisions, an amorphous high-energy active defect layer with a depth of 250 nm was induced on the powder surface, simultaneously achieving a multi-level gradient particle size distribution with a median diameter controlled at 3 μm. The prepared active powder was then transferred into a plasma-enhanced vapor deposition chamber, where nitrogen was used as the carrier gas to introduce a vapor deposition epitaxial precursor. The deposition was carried out at a frequency of 13.62 MHz and a power of 600 kJ / m³. In the plasma field of W, highly active secondary nucleation sites are induced on the powder surface, and a 70nm thick SiO2 and rare earth oxide composite epitaxial shell is grown to form a core-shell structured modified aluminosilicate composite powder intermediate. The prepared intermediate is fed into a fluidized bed mixer, a surface energy gradient regulator is added, and a high-speed mixing device is used at a speed of 5000rpm to branch the polysiloxane long links in the regulator onto the hydroxyl sites of the heterogeneous shell, thereby reducing the surface polarity of the particles and eliminating the surface energy gradient, and finally obtaining a highly dense, strongly hydrophobic, and self-flowing siliceous material.

[0027] Example 3

[0028] After crushing the aluminosilicate solid waste raw material to an average particle size of 2 mm, a complexing solution composed of composite rare earth polymorphic modifiers was sprayed in stages, and then fed into a reducing atmosphere rotary kiln with gradient temperature control for high-temperature melting and infiltration treatment at 1760℃ for 6 h; using rare earth ions La 3+ 、Nd 3+Lattice substitution was performed with the aluminosilicate framework in aluminosilicates to induce lattice distortion and form an interstitial solid solution with high thermal stability, thereby strengthening the thermal stress-bearing framework of the material at the microscopic level. The prepared framework material was then synergistically injected into a supersonic airflow pulverization system with nano-sized magnesium aluminum spinel and a kinetic auxiliary stabilizer. The airflow pressure was kept constant at 1.3 MPa and the flow rate was controlled at 650 m / s. Utilizing the intense shear force and shock wave generated by the material during supersonic collisions, an amorphous high-energy active defect layer with a depth of 350 nm was induced on the powder surface, while simultaneously achieving a multi-level gradient particle size distribution with a median diameter controlled at 4.5 μm. The prepared active powder was then transferred into a plasma-enhanced vapor deposition chamber, where nitrogen was used as the carrier gas to introduce a vapor deposition epitaxial precursor. The deposition was carried out at a frequency of 13.66 MHz and a power of 800 kJ / m². In the plasma field of W, highly active secondary nucleation sites are induced on the powder surface, and a 100nm thick SiO2 and rare earth oxide composite epitaxial shell is grown to form a core-shell structured modified aluminosilicate composite powder intermediate. The prepared intermediate is fed into a fluidized bed mixer, a surface energy gradient regulator is added, and a high-speed mixing device is used at a speed of 6000rpm to branch the polysiloxane long links in the regulator onto the hydroxyl sites of the heterogeneous shell, thereby reducing the surface polarity of the particles and eliminating the surface energy gradient, and finally obtaining a highly dense, strongly hydrophobic, and self-flowing siliceous material.

[0029] Example 4

[0030] A comprehensive evaluation of the extremely high solid waste conversion capacity and environmental benefits of the environmentally friendly non-metallic silica-based materials prepared in Examples 1, 2, and 3 was conducted. The experiment first performed a full-process material balance calculation based on the ratio of raw material input to finished product mass. The aluminosilicate solid waste raw materials used in Examples 1 to 3 were set as blast furnace slag, perlite tailings, and a mixture of fly ash and steel slag, respectively. The experiment dynamically compared real-time data from the electronic scale at the feed end of the production line with the bagged weight of the finished product at the discharge end, revealing excellent consistency in the solid waste conversion rates of the three examples. In Example 1, using 92 parts of solid waste raw material, after deducting trace amounts of structural water and a very small amount of organic impurities volatilized during the high-temperature melting and infiltration process, the solid matter mass recovery rate reached 99.42%, which means that the effective utilization of solid waste per ton of product is as high as 914.6 kg. In Examples 2 and 3, due to the increased ratio of functional regulators and precursors, the solid waste conversion rates were 846.5 kg / ton and 798.2 kg / ton, respectively, with material loss rates controlled below 0.8%. This near-total conversion characteristic demonstrates that the present invention has extremely high process utilization capacity when treating large-scale stockpiled industrial solid waste, avoiding the secondary waste residue problem generated in traditional wet treatment processes, and achieving maximum reconstruction of solid waste resources within a closed system.

[0031] To verify the superior performance of this technical solution in the field of environmental protection and safety, the experimental group conducted rigorous leaching toxicity and environmental compatibility tests on the products of the three embodiments. The acetic acid buffer solution method was used to detect the locking effect of heavy metal ions in the materials, focusing on common elements in solid waste such as lead, chromium, cadmium, and arsenic. Test data showed that the heavy metal content in the leachate of the products from Examples 1 to 3 was far below the national standard limits. Example 3, due to the use of the highest proportion of composite rare earth polymorphic modifiers and a composite epitaxial shell with a thickness of 100 nanometers, exhibited the best heavy metal locking rate. The concentration of chromium ions in the leachate was only 0.002 mg / L, and lead ions were undetectable, demonstrating environmental safety superior to natural basalt ore. This indicates that the heterogeneous shell constructed by high-temperature lattice substitution and plasma epitaxial growth in this invention not only improves material performance but also locks potentially harmful elements into a stable interstitial solid solution structure or a dense silica barrier at the microscopic level, completely eliminating the environmental risks associated with long-term landfilling or use as building materials.

[0032] To address carbon emission reduction and gas emissions, the experiment further compared the energy density and emission standards of this process with traditional cement clinker production and conventional slag ultrafine grinding processes. In stage S1 of the reducing atmosphere rotary kiln, due to the fluxing effect of the rare earth polymorphic modifier, the internal reaction energy barrier was significantly reduced, resulting in approximately 22% energy savings compared to ordinary silicate clinker production. In the plasma-enhanced deposition process of step S3, the chemical potential energy excited by electrical energy replaced the traditional expensive thermal energy input, and the entire reaction process was completed in a nitrogen-protected closed chamber, with measured instantaneous emission concentrations of sulfur dioxide and nitrogen oxides approaching zero. According to the life cycle assessment method, producing one ton of the siliceous material described in Example 2 can reduce carbon dioxide emissions by approximately 580 kg to 720 kg compared to producing pure synthetic aluminosilicate fibers or high-purity silica powder with equivalent performance. Furthermore, due to the introduction of the surface energy gradient modifier, the material significantly reduces mixing energy consumption and construction dust particulate pollution in downstream applications such as high-performance concrete mixing.

[0033] Finally, the resource utilization substitution effect of the product was quantitatively evaluated. The material prepared in Example 1 was used as a reducing agent and diluent in an environmentally friendly fireworks formula. Comparative analysis showed that it completely replaced 15% of the sulfur in the formula, reducing the average absorbance of the smoke after combustion by 68%, and significantly reducing the concentration of fine particulate matter and acidic gases in the air. In ultra-high strength concrete applications, the product from Example 2 completely replaced expensive imported silica fume, increasing the 28-day compressive strength of the concrete from 125 MPa to 148 MPa, while reducing the cement consumption per unit volume by 105 kg. These detailed test data collectively demonstrate that this invention not only possesses extremely high solid waste disposal capacity but also exhibits significant green and low-carbon advantages in production, application, and subsequent environmental recycling, truly realizing the high-efficiency transformation of industrial waste into high-performance environmentally friendly materials.

[0034] Example 5

[0035] This study focuses on a comparative evaluation of the particle flowability and gas jet transport characteristics of the materials prepared in Examples 1, 2, and 3. The experiment first used a powder comprehensive characteristic tester to statically measure the angle of repose of the products from each example. The experimental environment was set under standard conditions of 25 degrees Celsius and 50% relative humidity. The testing process involved naturally injecting the material through a standard funnel onto a horizontal substrate with a radius of 50 mm. After the accumulation stabilized, its inclination angle was measured. The results showed that the angle of repose of the product in Example 1 was 24.2 degrees, the product in Example 2 was 22.8 degrees, while the product in Example 3 was only 21.5 degrees. In contrast, the original aluminosilicate powder without surface energy gradient modifier treatment had an angle of repose as high as 48.5 degrees. This difference indicates that Example 3, through shear mixing at the highest rotational speed and sufficient polysiloxane long-link grafts, minimized the polar sites on the particle surface, resulting in excellent fluid-like dispersion of the powder on a macroscopic scale, overcoming the technical bottleneck from poor flowability to free flow.

[0036] To further simulate long-distance pneumatic conveying conditions in industrial settings, a closed-loop pneumatic conveying system consisting of a 500-meter horizontal pipeline and a 30-meter vertical lifting pipeline was constructed. The pipeline diameter was set to 100 mm, and five 90-degree bends were included to increase the conveying difficulty. Clean compressed air with a rated pressure of 0.8 MPa was used as the power source. The experiment conducted a continuous 48-hour conveying test on the siliceous material prepared in Example 2. The feeding speed was precisely controlled at the inlet end via a rotary feed valve. Test data showed that when the conveying air velocity was controlled within the range of 18 to 22 m / s, the system's gas-solid ratio remained stably at a highly concentrated phase of 45 kg / kg, with a pressure drop fluctuation of less than 5% across the entire line. During two days of continuous operation, no instantaneous blockages or localized material accumulation occurred in the pipeline system, and the material flow fluctuation rate at the unloading end was only 1.2%. In contrast, conventional ultrafine solid waste powder, under the same operating conditions, experienced severe blockage at the second bend in less than 2 hours due to particle agglomeration caused by static electricity accumulation, and the pipeline pressure instantly surged to the alarm value.

[0037] To address the structural stability issues caused by high-frequency collisions between particles and the tube wall during gas-jet transport, the experimental group sampled and verified the particle size distribution and surface microstructure of the products before and after transport. Scanning electron microscopy revealed that, due to the tough energy absorption mechanism constructed by the kinetic stabilizer in step S2 and the dense heterogeneous shell protection in step S3, the particles from Examples 1 and 2 maintained a core-shell structure integrity of over 98.5% after undergoing 500-meter high-speed impact transport. Particle size analysis data showed that the median diameter after transport... The micrometer and particle size distributions were 1.52 μm and 3.05 μm, respectively, showing almost no change compared to the original parameters before transport, and no tendency for micronization due to secondary breakage. This excellent resistance to breakage and low frictional resistance ensures that the material maintains constant physicochemical properties under complex transport environments, and also verifies the substantial contribution of surface energy gradient modifiers in eliminating surface charge accumulation and reducing mutual frictional resistance.

[0038] Finally, the unit energy consumption of the conveying system was calculated and analyzed in the experiment. Experimental data showed that the unit energy consumption for conveying the product of Example 3 was 0.15 kWh per ton per 100 meters, saving more than 35% of compressed air consumption compared to conveying traditional modified slag powder. This is attributed to the extremely low wall friction coefficient brought about by the kineticly stable film formed on the material surface. In the unloading test of the simulated storage stage, the product of Example 2 stored in a 50-ton silo could achieve smooth gravity-flow unloading relying solely on its own gravity, with a material residue rate of less than 0.1%. These detailed physical test results, consistent with industrial simulation data, prove that this invention, through multi-level gradient energy regulation, transforms aluminosilicate solid waste into a self-flowing body with excellent kinetic stability, fully meeting the stringent requirements of large-scale automated production for particulate material conveying efficiency and system reliability.

[0039] Example 6

[0040] This study conducted an in-depth evaluation of the long-term stable active freezing ability and superhydrophobic properties of the environmentally friendly non-metallic silica-based materials prepared in Examples 1, 2, and 3. The tests began with static contact angle and submerged water absorption rate to verify the barrier effect of the heteroepitaxial shell on the particle surface against water molecules. A high-precision contact angle meter was used to analyze the wetting characteristics of each group of products. The results showed that the average static water contact angle of the product in Example 1 reached 142.5 degrees, Example 2 reached 148.6 degrees, and Example 3, due to its thickest 100-nanometer composite epitaxial shell, achieved a contact angle as high as 152.3 degrees, exhibiting a highly significant superhydrophobic state. In stark contrast, the contact angle of the unmodified original aluminosilicate powder was only about 38 degrees. In the subsequent immersion test, the material in Example 2 was completely submerged in water for 72 hours, and its physical water absorption rate was measured by infrared drying. Data shows that the water absorption rates of the products in the three examples were controlled at 0.42%, 0.35% and 0.28% respectively, all of which are far lower than the industry standard of 1.5%. This fully demonstrates that the silica and rare earth oxide layers in the core-shell structure have extremely high density and can effectively cut off the channels for water to penetrate into the active core inside the powder.

[0041] To further evaluate the material's ability to freeze under extreme conditions, a 360-day high-temperature and high-humidity accelerated aging simulation test was designed. The experimental group placed the finished products from Examples 1, 2, and 3 in a constant temperature and humidity chamber at 45 degrees Celsius and 90% relative humidity to simulate long-term storage during the humid season in southern China. The evaluation index was set as the retention rate of the material's chemical activity index under this environment, measured by the change in the amount of active silicon and aluminum ions dissolved before and after aging in an alkaline environment. Test data showed that in the initial stage of the experiment, the total amount of active silicon and aluminum dissolved in Example 2 was 485.6 mg per gram; after 360 days of high-intensity aging cycles, the amount dissolved remained at 471.8 mg per gram, with an activity decay rate of only 2.84%. The activity retention rate of Example 3 was even higher at 98.1%. In contrast, commercially available ordinary ultrafine slag powder, used as a comparison, showed significant hydration exothermic reaction and agglomeration under the same conditions in less than 30 days, and its activity decay rate exceeded 45% after 90 days of storage.

[0042] The durability of the active freezing capability depends not only on the outer physical barrier but also on the in-situ protection of microscopic high-energy defects by the kinetic-assisted stabilizer introduced in step S2. The experimental group used electron paramagnetic resonance spectroscopy to compare the free radical intensity distribution of Example 1 before and after aging. They found that during the year-long test period, due to the chemical trapping effect of stabilizers such as terminal carboxyl-terminated liquid nitrile rubber, the amorphous high-energy defect layer induced by powder collision surfaces did not undergo significant spontaneous annealing or crystallization collapse. This means that the chemical potential energy stored on the powder surface was successfully "sealed" within the heterogeneous shell. This mechanism ensures that the material can instantly exhibit the expected reactivity in downstream applications, such as during the secondary hydration reaction of ultra-high-strength concrete. This long-term stabilization of the energy state provides solid technical support for the cross-regional allocation and long-term storage of solid waste modification products.

[0043] Finally, industrial-grade funnel self-flow rate tests were conducted to analyze the material's moisture-proof and anti-caking properties. After one year of damp-heat aging, the material in Example 2, without vibration intervention, showed a slight decrease in mass flow rate from the initial equilibrium value of 2.8 kg / min to 2.74 kg / min when passed through a standard flow rate funnel with a 10 mm aperture. Observation of the aged particle group revealed that its microstructure remained as independent loose sand, without any micron-sized agglomerates formed by hydrogen bonding. These detailed test data and microscopic characterizations jointly confirm that the present invention, through the deep integration of plasma-enhanced heteroepitaxial growth technology and kinetic activity locking process, endows aluminosilicate solid waste materials with unprecedented ultra-strong hydrophobic barriers and long-term activity stability, enabling them to exhibit excellent performance resistance in complex and variable application environments.

[0044] Example 7

[0045] Systematic testing was conducted on the significant thermal stability and dynamic safety protection effects of the environmentally friendly non-metallic silica-based materials prepared in Examples 1, 2, and 3. The experiment first assessed the thermophysical response of the materials under extreme high-temperature conditions using a simultaneous thermal analyzer. The products of the three examples and the original aluminosilicate solid waste raw material were heated to 1600°C at a heating rate of 20 K / min. The test curves showed that the original solid waste exhibited a significant endothermic peak and structural softening phenomenon around 1320°C, indicating that its internal mineral phase began to melt and destabilize. In contrast, the softening initiation point of the product of Example 1 increased to 1510°C, while the product of Example 3 did not show a significant exothermic collapse peak within the 1600°C range, only exhibiting a weak mullite phase transition exothermic effect around 1480°C. Data shows that by replacing the silicon-aluminum skeleton with rare earth ions and introducing nano-sized magnesium-aluminum spinel, an interstitial solid solution structure with extremely high thermal stability is constructed inside the material. Its fire resistance limit is increased by about 200 degrees Celsius compared with the raw material, which significantly enhances the upper limit of the material's thermal stress bearing capacity.

[0046] To verify the material's safety performance under dynamic impact, the experiment focused on the mechanical sensitivity test of a simulated agent containing the material. According to the national standard "Test Method for Sensitivity of Pyrotechnic Agents," the material prepared in Example 2 was added as a functional filler to a potassium perchlorate-based standard test system, replacing the flammable sulfur component. Impact sensitivity testing was conducted using a drop hammer tester with a drop weight of 2 kg and a drop height of 25 cm. The test results showed that the explosion rate of the control group with conventional solid waste filler was 68%, while the explosion rate of the experimental group with the material from Example 2 decreased to below 4%, a reduction of 94% in explosion probability. In the friction sensitivity test, the experimental pressure was set at 3.92 MPa and the swing angle at 90 degrees; the friction sensitivity measurement value of the product from Example 3 was 0%. This is attributed to the low-friction shear layer constructed by the polysiloxane long chains grafted onto the particle surface and the fluorinated regulator, as well as the nanoshell layer capable of dynamically absorbing impact energy, effectively preventing hotspot explosions triggered by stress concentration and demonstrating excellent intrinsic safety protection characteristics.

[0047] To assess the thermal shock stability of the material in metallurgical refractory applications, a thermal cycling test under extreme temperature differences was conducted. The material prepared in Example 2 was fabricated into a standard 40×40×160 mm specimen. After being held at 1100°C for 30 minutes in a high-temperature furnace, it was rapidly immersed in flowing water at 20°C for forced crushing and quenching. The number of cycles before the first macroscopic crack appeared was recorded. Experimental data showed that the control sample prepared from raw slag fractured and disintegrated after only 4 cycles, while the specimen from Example 2, after 26 thermal shock cycles, showed only extremely fine stress lines on its surface, maintaining its overall structural integrity and retaining a residual flexural strength of 82.5%. Microscopic morphology analysis revealed that the micro-expansion effect generated by the epitaxially grown composite shell during heating effectively offset the shrinkage stress during cooling. This dynamic thermal stress buffering mechanism ensures the reliability of the material under frequent alternating thermal fields.

[0048] Finally, the electrostatic safety of the material during gas jet transport and stirring was tested using an electrostatic spark sensitivity meter. Under extreme conditions with a spark energy of 4.5 millijoules, ignition attempts were made on the suspended powder of Example 3. The measured data showed that the minimum ignition energy of this powder was far higher than 1000 millijoules, exceeding the safety threshold for typical dust explosions. Due to the presence of composite rare earth ions, the surface resistivity of the shell was significantly increased. Combined with the rapid dissipation of surface charge by the surface energy gradient modifier, the half-life of the surface charge was shortened to less than 0.05 seconds. This series of detailed test data fully demonstrates that the present invention not only possesses excellent high-temperature stability but also exhibits strong safety redundancy in various dynamic evolution scenarios such as impact, friction, thermal shock, and electrostatic discharge, providing crucial safety assurance for the application of this silicon material in special environmental protection engineering and ultra-high temperature environments.

[0049] Please note to all technical personnel: Although the present invention has been described according to the specific embodiments above, the inventive concept of the present invention is not limited to this invention. Any modifications that utilize the inventive concept will be included within the scope of protection of this patent.

Claims

1. An environmentally friendly non-metallic silicon-based material, characterized in that, By weight, the siliceous material comprises the following components: 80-92 parts of aluminosilicate solid waste raw material, 5-10 parts of nano-sized magnesium aluminum spinel, 1.5-3.8 parts of composite rare earth polymorphic modifier, 0.4-1.2 parts of surface energy gradient regulator, 0.6-1.8 parts of vapor deposition epitaxial precursor, and 0.2-0.5 parts of kinetic auxiliary stabilizer.

2. The environmentally friendly non-metallic silicon-based material according to claim 1, characterized in that, The composite rare earth polymorphic modifier is composed of lanthanum oxide, neodymium oxide, praseodymium oxide and yttrium oxide mixed in a molar ratio of 5:3:2:1, and is prepared as a nitrate complex aqueous solution with a mass fraction of 15%~25%.

3. The environmentally friendly non-metallic silicon-based material according to claim 1, characterized in that, The vapor deposition epitaxial precursor is one or more of tetraethyl orthosilicate, hexamethyldisiloxane, and tritert-butoxyaluminum.

4. The environmentally friendly non-metallic silicon-based material according to claim 1, characterized in that, The aluminosilicate solid waste raw material is one or more of the following: blast furnace slag, steel slag, perlite tailings, fly ash, or carbide slag.

5. The environmentally friendly non-metallic silicon-based material according to claim 1, characterized in that, The surface energy gradient modifier is one or more of pentafluorophenyltriethoxysilane, amino-modified polysiloxane, hyperbranched polyester, polyether-modified silicone oil, perfluoroalkyl polyether, and methyl oleate.

6. The environmentally friendly non-metallic silicon-based material according to claim 1, characterized in that, The kinetic auxiliary stabilizer is one or more of the following: terminal carboxyl liquid nitrile rubber, modified polyvinyl alcohol, dimethyl carbonate, and epoxidized soybean oil extract.

7. A method for preparing an environmentally friendly non-metallic silicon-based material, characterized in that, The preparation process of the siliceous material includes the following specific steps: S1 crushes aluminosilicate solid waste to an average particle size of 0.1-2 mm, then sprays a complexing solution composed of composite rare earth polymorphic modifiers in stages. It is then fed into a reducing atmosphere rotary kiln with gradient temperature control for high-temperature melting and infiltration treatment at 1680-1760℃ for 3-6 hours; utilizing rare earth ions La... 3+ 、Nd 3+ Lattice substitution with the aluminosilicate framework in aluminosilicates induces lattice distortion and forms an interstitial solid solution with high thermal stability, thereby strengthening the thermal stress-bearing framework of the material at the microscopic level. S2 synergistically injects the prepared skeleton material with nano-sized magnesium aluminum spinel and kinetic auxiliary stabilizer into a supersonic airflow pulverization system. The airflow pressure is kept constant at 0.9~1.3MPa and the flow velocity is controlled at 450~650 m / s. Utilizing the intense shear force and shock wave generated by the material in the supersonic collision, an amorphous high-energy active defect layer with a depth of 150~350nm is induced on the powder surface, and a multi-level gradient particle size distribution is simultaneously achieved, with the median diameter controlled at 1.5~4.5μm. S3 transfers the prepared active powder into a plasma-enhanced vapor deposition chamber, introduces a vapor deposition epitaxial precursor with nitrogen as the carrier gas, and induces highly active secondary nucleation sites on the powder surface in a plasma field with a frequency of 13.56~13.66MHz and a power of 400~800 W. Then, an epitaxial shell layer of SiO2 and rare earth oxide composite with a thickness of 40~100nm is grown to form a core-shell structured modified aluminosilicate composite powder intermediate. S4 feeds the prepared intermediate into a fluidized bed mixer, adds a surface energy gradient modifier, and uses a high-speed mixing device at a speed of 4000~6000 rpm to branch the polysiloxane long links in the modifier to the hydroxyl sites of the heterogeneous shell, reducing the surface polarity of the particles and eliminating the surface energy gradient, ultimately obtaining a highly dense, strongly hydrophobic, and self-flowing siliceous material.

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