A slow-release trace element hydrotalcite-microorganism composite functional particle and application thereof

Abstract

The application relates to the technical field of functional composite materials, and discloses a kind of slow-release trace element hydrotalcite-microorganism composite functional particles and application, comprising: ZnMgAl hydrotalcite functional core, microbial component and interface transition layer between the functional core and the microbial component, the functional core has amorphous wrinkle edge and asymmetric lattice defect, intercalation has trace element anion between layers, so that the physical binding energy between anion and layer plate presents non-uniform gradient distribution, the microbial component contains interpenetrating network structure composed of polyvinyl alcohol and sodium alginate, the interface transition layer is formed by silane coupling agent grafting, the application utilizes asymmetric lattice defect to construct energy gate, cooperates with the release path of interface transition layer construction, constrains trace element desorption kinetics, composite particles realize uniform speed supply of trace element in liquid phase matrix environment, and improve the service stability of material in ion background fluctuation environment.

Description

Technical Field

[0001] This invention relates to a hydrotalcite-microbial composite functional particle with slow-release trace elements and its application, belonging to the field of functional composite materials technology. Background Technology

[0002] Currently, the stable replenishment of trace elements to maintain microbial enzyme activity is fundamental to ensuring system operating efficiency. Trace elements are loaded onto functional particles using physical encapsulation or surface adsorption processes to provide the nutrients required for microbial metabolism. Industrial wastewater generally has the physical characteristics of high salinity and frequent fluctuations in pH. Traditional carriers are affected by electrolyte shock and competitive replacement of anions during service. Increasing the thickness of the coating layer to delay component loss increases the mass transfer resistance between microorganisms and the external matrix, resulting in a fundamental constraint between prolonged slow-release period and decreased metabolic efficiency.

[0003] Existing hydrotalcite-like carriers form thermodynamically stable structures during crystal maturation. Their layered energy level distribution is uniform, but they lack specific physical locking mechanisms. When faced with high-intensity ion impacts, they exhibit synergistic desorption characteristics. Furthermore, the organic shell and inorganic core are physically adhered together, leading to interfacial peeling and structural instability risks under strong hydraulic shear conditions. Research on improving carrier performance focuses on adjusting the overall pore size or morphology, but lacks precise constraints on the surface interfacial energy level distribution and slow-release kinetics. For example, Chinese invention patent CN118389368B discloses a method and application for preparing microbial materials loaded with sildenafil and calcium-iron hydrotalcite, utilizing the layered structure of hydrotalcite to achieve microbial loading. Essentially, this does not deviate from the scope of physical adsorption or overall encapsulation. The lack of a strong covalent anchoring structure between the inorganic core and biological components results in poor interfacial stability under industrial-grade high-intensity hydraulic shear conditions, leading to coating layer detachment and functional failure.

[0004] Therefore, how to regulate the surface energy level distribution of hydrotalcite-like plates and construct a chemically stable interface anchoring structure to achieve confined and uniform release of trace elements while maintaining efficient mass transfer has become the technical problem to be solved by this invention. Summary of the Invention

[0005] To address the problems mentioned in the background art, the technical solution of the present invention is as follows: a hydrotalcite-microbial composite functional particle for slow-release trace elements, comprising:

[0006] Hydrotalcite-like functional core, microbial components and located in An interfacial transition layer between the hydrotalcite-like functional core and the microbial components; The molar ratio of metal cations in the hydrotalcite-like functional core satisfies for to to ; The hydrotalcite-like functional core has amorphous wrinkled edges and asymmetric lattice defects formed by the step perturbation of hydrogen ion concentration during the aging stage.

[0007] The interlayer intercalation of the hydrotalcite-like functional core contains trace element anions, and the asymmetric lattice defects cause the physical binding energy between the trace element anions and the layers to exhibit [variable characteristics]. to Non-uniform gradient distribution;

[0008] The microbial component includes bioactive units and an interpenetrating network structure for encapsulating the bioactive units. The interpenetrating network structure is composed of polyvinyl alcohol and sodium alginate crosslinked together.

[0009] The interface transition layer is formed by a silane coupling agent. The active hydroxyl sites at the edge of the layered structure of the hydrotalcite-like functional core are grafted in situ, and the thickness of the interfacial transition layer is [missing information]. to In a liquid medium environment, the interfacial transition layer, interpenetrating network structure, and amorphous wrinkled edges together constitute a confined release pathway for trace element anions. The amorphous wrinkled edges, in particular, provide radial... to The morphology within the depth creates mass transfer resistance for ion exchange;

[0010] The gradient binding energy generated by asymmetric lattice defects constrains the desorption rate of trace element anions, causing the trace element anions to be released at a uniform and slow rate throughout the material's service life.

[0011] Preferred, During the preparation process, the hydrotalcite-like functional core... to At the aging temperature, an intensity of [value missing] is introduced into the reaction system. to The hydrogen ion concentration step perturbation induces Asymmetric lattice defects are generated inside the hydrotalcite-like material. The interlayer spacing of the hydrotalcite-like functional core is to .

[0012] Preferably, the silane coupling agent used in the interface transition layer is... The interface transition layer is in The hydrotalcite-like functional core is located at a temperature below In liquid slurry, through the active hydroxyl sites at the edge of the plate and The tortuosity of the confined release pathway generated by the dehydration condensation reaction of ethanol solution is regulated by the steric hindrance of the organic long chain of the silane coupling agent.

[0013] Preferably, the bioactive units include denitrifying thiobacilli and denitrifying polyphosphate-accumulating bacteria; the microbial components and The weight ratio of the hydrotalcite-like functional core is to The weight ratio of polyvinyl alcohol to sodium alginate in the interpenetrating network structure is: to .

[0014] Preferably, the particle size of the composite functional particles is [missing value]. to It has a multi-level pore size distribution structure inside, in which The micropore size formed by the hydrotalcite-like functional core is to The large aperture formed by the interpenetrating network structure is to Micropores and macropores are interconnected to form mass transfer channels for trace element anions.

[0015] Preferably, the cumulative release rate of trace elements in the composite functional particles The following relationship must be satisfied: ,in, for Cumulative release percentage at any given time The sustained release rate constant is determined by the defect density of the asymmetric lattice defects. For the service life of materials in a liquid medium environment, Let be the diffusion exponent for releasing path constraints from the bounded domain, and satisfy to When the background ion concentration of the liquid medium environment is to At that time, the release kinetics curve of trace elements conforms to the quasi-zero-order release model controlled by energy order.

[0016] Preferred, The crystallinity of the hydrotalcite-like functional core is to Furthermore, the surface free energy at the edges of amorphous wrinkles is higher than that of... Central area of ​​hydrotalcite-like slab to The fluctuating electron cloud density at the edges of amorphous wrinkles forms physical damping against trace element anions.

[0017] Preferably, the trace element anions include at least one of molybdate ions, cobalt ion complex anions, or selenate ions, and the trace element anions are distributed in a manner of ion exchange. The interlayer of the hydrotalcite-like functional core, and trace element anions in The mass percentage of hydrotalcite-like functional core is to .

[0018] Preferred, The surface negative charge density of the hydrotalcite-like functional core is determined by the molar ratio. and Adjustment of the ratio; when molar ratio in to When fluctuating within a range, The electrostatic affinity between the hydrotalcite-like functional core and the microbial components changes accordingly to maintain the microbial components at a liquid flow rate lower than [a certain value]. The interface stability during the process, and the uniform slow release period of trace elements is not less than During the material's service life, the volume expansion rate of the composite functional particles is lower than that of the composite functional particles. Used to maintain interface transition layers, interpenetrating network structures and Mechanical anchoring force between the functional cores of hydrotalcite-like materials.

[0019] Application of a slow-release trace element-like hydrotalcite-microorganism composite functional particle: This particle is used as a slow-release trace element additive in a liquid matrix environment.

[0020] Compared with the prior art, the beneficial effects of the present invention are:

[0021] 1. In hydrotalcite-microbial composite functional particles, by selecting a specific molar ratio of zinc, magnesium, and aluminum metal cations, and combining this with the hydrogen ion concentration step disturbance introduced during the aging stage, asymmetric lattice defects are induced inside the hydrotalcite-like layers. This breaks the uniformity of charge distribution in traditional material layers, causing the binding energy between the intercalated trace element anions and the layers to exhibit a non-uniform distribution. This constructs an energy gate for ion release. When the particles are in a complex hydrodynamic environment with high salinity or drastic fluctuations in ion background, the gradient binding energy generated by the lattice distortion can suppress the explosive loss caused by competitive exchange of external ions. This transforms the traditional dissolution and diffusion mode into a confined release mode controlled by energy levels, ensuring a uniform supply of trace elements throughout their entire life cycle.

[0022] 2. By utilizing the dehydration and condensation reaction of silane coupling agents in a low-water environment, functional long chains are in situ grafted onto the active hydroxyl sites at the edge of the hydrotalcite-like layer, forming covalent connections with the outer polymer network. This transformation from physical encapsulation to chemical pinning establishes a stable interfacial bridge between the inorganic core and the organic network, enhancing the interfacial shear strength of the particles. Under conditions of strong hydraulic shear and hydrocyclone scouring, such as in biochemical reaction systems, the chemically anchored structure can resist the peeling stress of the phase interface, maintaining the integrity and physical continuity of the composite particle structure. This solves the technical problem of conventional functional particles being prone to core failure due to coating layer detachment during long-term service.

[0023] 3. An interpenetrating network structure composed of sodium alginate and polyvinyl alcohol, combined with a hydrotalcite-like core with acid-base buffering capacity, provides a self-regulating habitat for microorganisms. The physical entanglement generated during the calcium ion crosslinking process of polyvinyl alcohol and sodium alginate effectively inhibits the swelling tendency of the organic matrix in a high-phosphorus wastewater environment. Combined with the chemical traction effect of the interfacial transition layer, the long-term stability of the pore size of the mass transfer channel is achieved. This synergistic effect of the multi-level structure not only ensures the dynamic adaptation between the release rate of trace elements and the needs of microbial enzymatic reactions, but also eliminates the inhibitory effect of extreme temperature or acid-base fluctuations on microbial activity by maintaining the chemical potential balance of the microenvironment, thereby improving the overall engineering stability of the application material. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the three-layer assembly structure of composite particles with asymmetric lattice defects and the energy gate control of the present invention;

[0025] Figure 2 This diagram illustrates the low-temperature dehydration polycondensation molding process and intermolecular covalent bonding mechanism of the interface transition layer of this invention. Detailed Implementation

[0026] To make the technical problems to be solved, the technical solutions and the beneficial effects of the present invention clearer, the present invention will be described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are intended to explain the present invention and are not intended to limit the scope of protection of the present invention.

[0027] This invention provides a hydrotalcite-microbial composite functional particle for slow-release trace elements and its application, including particles containing amorphous wrinkled edges. The system comprises a hydrotalcite-like functional core, an interfacial transition layer formed by grafting with a silane coupling agent, and an outermost microbial component. The microbial component includes bioactive units and an interpenetrating network structure for encapsulating these units. The interpenetrating network structure is composed of polyvinyl alcohol and sodium alginate crosslinked together. In processes targeting the treatment of high-salinity industrial wastewater, the background ion concentration is typically... to Within a certain range, competitive replacement by external anions can lead to a rapid loss of trace elements from conventional carriers. To address this objective obstacle in this application scenario, the present invention... During the preparation process, the hydrotalcite-like functional core is... to At the aging temperature, an intensity of [value missing] is introduced into the reaction system. to The hydrogen ion concentration step perturbation induces Asymmetric lattice defects are generated inside the hydrotalcite-like material. The molar ratio of metal cations in the hydrotalcite-like functional core satisfies for to to Asymmetric lattice defects cause the physical binding energy between trace element anions intercalated in the interlayer and the layers to exhibit [variable characteristics]. to The non-uniform gradient distribution of trace element anions includes at least one of molybdate ions, cobalt ion complex anions, or selenate ions, with a mass percentage in the functional core of [missing information]. to The energy gate formed by this gradient binding energy suppresses the explosive desorption induced by external ions, achieving a uniform supply of trace elements in a liquid matrix environment; an intensity marker is introduced. Quantifying the step perturbation of hydrogen ion concentration, defining , This is to ensure that the system instantly reaches its peak hydrogen ion molar concentration after the acid injection pulse. This refers to the molar concentration of hydrogen ions in the aging system under thermodynamic equilibrium conditions; specifically, the concentration is injected into the reaction system via a high-precision metering pump. to Sulfuric acid solution, control the injection time within to Between, making the system Value generation to Instantaneous unit decrease, inducement Asymmetric distortion occurs in the hydrotalcite-like lattice; the physical binding energy gradient distribution is obtained through stepwise ion exchange experiments. The equation is obtained by reverse calculation, specifically in to of Measurement of the desorption rate constant of trace elements at different temperature points in solution background ,use Reciprocal of temperature Linear fitting is used to determine the desorption activation energy based on the slope of the fitted curve. As a criterion for measuring physical binding energy.

[0028] The strong hydraulic shearing and hydrocyclone scouring in biochemical reaction systems can easily lead to the detachment of the functional particle coating. At the active hydroxyl sites on the edge of the layered structure of the hydrotalcite-like functional core, silane coupling agents are in situ grafted to form an interfacial transition layer. The silane coupling agents used are... -aminopropyltriethoxysilane During preparation, The hydrotalcite-like functional core is located at a temperature below In liquid slurry, the water content of the system is controlled to be below a certain mass fraction. Through the active hydroxyl sites at the edge of the lamination and The dehydration condensation reaction of ethanol solution produces a product with a thickness of to The interface transition layer, through chemical anchoring, establishes a stable interfacial bridge between the inorganic core and the organic network, maintaining the microbial components at liquid flow rates below a certain threshold. Interface stability at low moisture content; in-situ grafting of the interface transition layer at low moisture content The procedure is performed in an anhydrous ethanol system, after which the product is washed and dried to constant weight. Water-like double hydroxide functional core input temperature to Liquid slurry, add concentration of The ethanol solution is controlled to maintain the system temperature within a low-temperature range below the silanol hydrolysis rate, so that... The ethoxy group reacts directly with the active hydroxyl sites at the edge of the lamination to undergo a dehydration condensation reaction to generate... covalent bond, Representing the metal atoms of the layer plates; after forming a chemically anchored structure, the steric hindrance effect of the silane coupling agent molecular chain segments is used to adjust the tortuosity of the confined release path, enhance the interfacial shear strength between the microbial components and the inorganic core, and maintain the volume expansion rate of the composite particles below a certain level during the service life. To ensure that the mass transfer channel operates at a liquid phase flow rate lower than [the specified value]. To ensure physical continuity and further optimize the release kinetics of trace elements throughout their life cycle, thereby improving the survival rate of microorganisms under fluctuating acid-base conditions, the microbial components of this invention employ an interpenetrating network structure composed of polyvinyl alcohol and sodium alginate. The bioactive units include denitrifying thiobacilli and denitrifying polyphosphate-accumulating bacteria. The microbial components and... The weight ratio of the hydrotalcite-like functional core is to The weight ratio of polyvinyl alcohol to sodium alginate in the interpenetrating network structure is: to In a liquid medium environment, the interfacial transition layer, interpenetrating network structure, and amorphous wrinkled edges together constitute a confined release pathway for trace element anions. Among them, the amorphous wrinkled edges radially... to The morphology within the depth range creates mass transfer resistance for ion exchange; the particle size of the composite functional particles is... to It has a multi-level pore size distribution structure inside, in which The micropore size formed by the hydrotalcite-like functional core is to The large aperture formed by the interpenetrating network structure is to .

[0029] To achieve energy control over the desorption pathway of trace elements, The crystallinity of the hydrotalcite-like functional core is set at to Within this range, crystallinity is controlled by the nucleus growth kinetics of the aging stage, through... The ratio of the diffraction peak area to the diffuse scattering background area is obtained by measuring the X-ray diffraction instrument; when the crystallinity is lower than At that time, the degree of order in the lamellar structure was insufficient to support the long-term ion exchange pressure, while the degree of crystallinity exceeded... This leads to excessively high coordination saturation of the edge hydroxyl groups, inhibiting the formation of amorphous wrinkle edges and the generation of their surface energy gradients; the surface free energy at the edges of amorphous wrinkles is higher than... Central area of ​​hydrotalcite-like slab to This energy gradient is generated by the non-equilibrium arrangement of atoms at the edge of the laminations during the cooling process. It is calculated using a dynamic contact angle meter to determine the wetting behavior of liquids of different polarities on the particle surface and in conjunction with the Owens-Wendt equation. The resulting surface free energy gradient alters the electron cloud distribution at the lamination edges, creating a physical damping effect against trace element anions. A cooling kinetics compensation procedure is used to control the morphology of the lamination edges, constructing amorphous wrinkled edges. The flow rate of the circulating cooling medium is adjusted through a heat exchange module to control the cooling rate of the aged slurry. Constant to until the slurry temperature drops to The following describes the radial depth of amorphous wrinkle edges, calibrated using a high-resolution transmission electron microscope, specifically after drying. The core was embedded in a hydrotalcite-like functional resin and the thickness was measured using an ultrathin slicer. to Thin slices were observed, and the atomic arrangement at the edge of the plates was analyzed. The width of the edge region where long-range ordered structure disappeared was statistically determined. to Topographic resistance depth; regional fluctuation distribution of electron cloud density forms physical damping against trace element anions, reducing the diffusion index. In to Scope; cumulative release rate of trace elements in composite functional particles The following relationship must be satisfied: ,in, for Cumulative release percentage at any given time; The sustained release rate constant is determined by the defect density of the asymmetric lattice defects; The service life of materials in a liquid medium environment; Let be the diffusion exponent for releasing path constraints from the bounded domain, and satisfy to ;exist During the service life of the above materials, the volume expansion rate of the composite functional particles is less than [percentage missing]. This synergistic effect of the multi-level structure not only ensures the matching of trace element release rate with the metabolic needs of microorganisms, but also reduces the acid-base buffering capacity of industrial wastewater through the hydrotalcite-like core. Fluctuations inhibit microbial activity.

[0030] Example 1: In a biochemical reaction system for treating high-salinity industrial wastewater, the mass concentration of sodium chloride in the liquid phase matrix is ​​maintained at... Affected by fluctuations in upstream water inflow, the reaction system Value at to The frequent alternation between these phases results in a shear rate of up to [missing information]. This operating condition causes a burst release of conventional trace element carriers due to competitive anion displacement, resulting in metabolic disorders in downstream microorganisms; using the aforementioned technical solution, a method for preparing... A hydrotalcite-like functional core in which the molar ratio of metal cations satisfies for During the aging stage, an intensity of [unclear] was introduced. The hydrogen ion concentration step perturbation generates asymmetric lattice defects within the inorganic layer. These asymmetric lattice defects lock the physical binding energy between the molybdate anion and the layer at a certain point. The nearby non-uniform gradient region, due to The hydrotalcite-like functional core has amorphous wrinkled edges, which are formed by washing and drying. The core of the hydrotalcite-like functional material contains Interface modification was performed on anhydrous ethanol slurry. The modified core was then mixed with premixed polyvinyl alcohol and sodium alginate solution according to... The weight ratio at a stirring rate of Mix in a mixer Through a diameter of The pore size is used for drop extrusion and enters the mass percentage concentration. The particles were formed in a calcium chloride curing bath to obtain particles with a diameter of [missing value]. to Composite functional particles.

[0031] In this composite system with a multi-level hybrid structure, the binding energy distribution generated by asymmetric lattice defects and the confined release paths formed by the interface transition layer and the interpenetrating network structure produce a synergistic effect, and the amorphous wrinkle edges radially... Within a certain depth, mass transfer resistance for ion exchange is generated, affecting the diffusion index of trace element anions. Stable at Actual cumulative release rate With service life The evolution conforms to the relational formula ,in for Cumulative release percentage at any given time The sustained-release rate constant is For the service life of materials, The diffusion index is used, and this mechanism changes the path of relying on increasing the coating thickness to delay release, allowing the system to maintain mass transfer efficiency while extending the trace element release period beyond that of the standard. The composite functional particles operate continuously under the above conditions. Afterwards, its volume expansion rate is No interfacial separation between microbial components and the inorganic core occurred, and the denitrification efficiency of the biochemical system remained at [value missing]. In summary, the uniform supply of trace elements ensures the continuous stability of microbial enzymatic reactions.

[0032] Example 2: Experimental verification of the release stability and interfacial stability of composite functional particles under different ionic strength backgrounds; the experimental platform used an effective volume of The continuous stirring biochemical reaction simulation device uses data from physical experimental tests; trace element concentrations are measured using inductively coupled plasma optical emission spectrometry (ICP-OES), with a detection accuracy of [insert accuracy here]. The sampling period is set to The technical consideration in determining the sampling period lies in the trade-off between capturing transient concentration gradients of trace elements and maintaining the continuous operational stability of the biochemical system; the signal-to-noise ratio of the actively superimposed sample in the experimental influent is [value missing]. The chemical oxygen demand (COD) is simulated based on upstream process fluctuations, and the influent is controlled. Value at to The range exhibits random periodic fluctuations; the experiment includes the present invention's sample group, control group, and out-of-range control group; sample groups 1 to 3 correspond to the median, lower limit, and upper limit of the preparation process parameters, respectively; sample groups 6 and 7 correspond to the conditions where the hydrogen ion concentration step disturbance intensity is below the lower limit and above the upper limit, respectively; sample groups 8 and 9 are used to investigate the effect of sodium chloride gradient concentration on steady-state release; control groups 4 and 5 represent the technical solutions with a disturbance intensity of 1.0, no lattice defects, physical coating, and no transition layer, respectively; sample group 10 is a purely physically embedded sample from the prior art; the preparation procedure for sample group 1 includes: according to Zinc, magnesium, and aluminum metal salt solutions were prepared in molar ratios and then prepared by co-precipitation. The hydrotalcite-like functional core, in Lower aging and introduce strength of The hydrogen ion concentration step perturbation; the dried kernel is then placed into a container containing of In ethanol slurry, at a temperature of And the system's moisture content mass fraction is lower than Grafting in an environment In practice, the tortuosity of the confined release path is adjusted by controlling the grafting density of the silane coupling agent at the edge of the layer. When the concentration of the coupling agent or the grafting time in the reaction system is adjusted, the number of silane coupling agent molecules adsorbed and reacted on the active hydroxyl sites changes, causing the organic long chains extending at the edge of the inorganic layer to undergo a conformational transformation from loose coiling to close arrangement in space. The close arrangement of molecules increases the steric hindrance effect, requiring trace element anions to bypass more complex organic molecular chain barriers when diffusing outward. The tortuosity of the mass transfer path increases accordingly. Thus, the tortuosity of the diffusion path is precisely controlled by adjusting this process parameter, allowing the modified core and microbial slurry to be processed according to... The weight ratio in Mixing at a certain speed, the weight ratio of polyvinyl alcohol to sodium alginate in the microbial slurry is: ; through a diameter of The nozzle with The mass percentage concentration is obtained by uniformly dripping in. of In the curing bath, after molding, a particle size of [missing value] is obtained. to The preparation procedures for composite functional particles, samples 2 to 3, 6 to 9, and control groups 4 to 5, were basically the same as those for sample 1. The only difference in their preparation procedures was the setting of key parameters listed in Table 1, such as the hydrogen ion concentration step disturbance intensity, the NaCl concentration in the test environment, or whether to introduce lattice disturbance and whether to perform silane coupling agent grafting transition layer according to the control settings. Other process parameters, such as the molar ratio of raw materials, aging temperature, grafting procedure, material mixing ratio, and molding and curing conditions, were strictly consistent with those of sample 1. The preparation procedure for sample 10 was the conventional pure physical embedding method in the existing technology, that is, omitting the hydrogen ion disturbance and silane coupling agent grafting steps in the aging stage, and directly physically mixing the conventional unmodified hydrotalcite core with polyvinyl alcohol-sodium alginate microbial slurry and then dripping and curing it. The specific test process and measurement results are shown in Table 1.

[0033] Table 1: Performance Comparison of Composite Functional Particles under Different Working Conditions and Process Parameters

[0034]

[0035] Analyzing the measurement results in Table 1, the diffusion index of samples 1 to 3 Stable at to Within the specified range, it indicates that the release kinetics are controlled by an energy gate generated by asymmetric lattice defects; data from sample group 6 show that when the perturbation intensity is below the lower limit, The value increases to The sustained-release performance decreased; data from sample group 7 showed that excessively high perturbation intensity led to an increase in the interfacial peeling rate, which was due to the stress within the laminate caused by excessive lattice distortion disrupting the stability of the chemical anchoring structure; the cumulative release rate difference between sample groups 8 and 9 was [missing data]. This confirms that the solution of the present invention is effective. to It possesses ion exchange resistance under high salt concentration gradients; the higher interfacial peeling rate of control group 5 demonstrates the structural support role of the interfacial transition layer under hydraulic shear conditions; the cumulative release rate of trace elements in the composite functional particles... Over time The evolution satisfies the relation ;in, for Cumulative release percentage at any given time; The sustained release rate constant is determined by the asymmetric lattice defect density; Service life, unit: ; The diffusion index is denoted as ; the diffusion index of sample group 1 measured in the experiment is . This corresponds to the quasi-zero-order kinetic characteristics under the constraint of the confined release path, ensuring the dynamic adaptation of the trace element supply rate to the microbial denitrification metabolic demand.

[0036] Example 3: This example combines Figures 1 to 2 Instructions for the application of a slow-release trace element-like hydrotalcite-microbial composite functional particle, such as... Figure 1 As shown, the composite functional particles consist of a three-layer structure. The ZnMgAl-type hydrotalcite functional core is located at the center of the structure. It contains asymmetric lattice defects and amorphous wrinkled edges, and trace element anions are intercalated between the layers. It is connected to the interface transition layer through chemical anchoring. It is formed by in-situ grafting of silane coupling agent and connects to the active hydroxyl sites on the edge of the layer. Its thickness is 2nm to 8nm. The interface transition layer binds to the microbial components outward through physical embedding and connection. The microbial components are composed of an interpenetrating network structure formed by cross-linking polyvinyl alcohol and sodium alginate and the bioactive units embedded in it. It constructs a confined release pathway based on a synergistic mechanism, including a physical binding energy with a non-uniform gradient distribution and values ​​ranging from 20.5kJ / mol to 45.8kJ / mol, and a mass transfer resistance generated radially by the amorphous wrinkled edges. Through the mechanism constraining the desorption kinetics, the trace elements are finally released in a uniform and slow-release state.

[0037] like Figure 2 As shown, regarding the construction process of the interface transition layer, the functional core is washed and dried to expose the active hydroxyl groups at the edge of the layer, thereby obtaining the active hydroxyl sites. Parallel to this, a 5wt% KH-550 ethanol solution is prepared in an anhydrous ethanol system, and the treated core is immersed in a temperature less than 10°C. In a low-temperature slurry with a water content of less than 0.5%, hydroxyl groups react with silane and ethoxy groups participate in the reaction. During the 2-hour grafting time, a dehydration condensation reaction occurs and Si-OM covalent bonds are formed, ultimately generating an interfacial transition layer with a thickness of 2 nm to 8 nm.

[0038] Example 4: In industrial wastewater deep treatment systems designed for ultra-long service lives, composite functional particles need to be... Maintaining a stable supply of trace elements during its service life, and the cumulative release rate Need to be in The following is the sustained-release rate constant. It needs to be controlled within to To determine the sustained-release rate constant during the preparation of composite functional particles, a range was defined to match the metabolic rate of bioactive units under low carbon-to-nitrogen ratio conditions. The value is determined. Initial input parameters for the hydrotalcite-like functional core; setting the molar ratio of zinc, magnesium, and aluminum metal cations to... ;exist At the aging temperature, the intensity of the hydrogen ion concentration step perturbation is controlled. To adjust defect density; to establish With constant The correlation between them was determined by the following calibration procedure in the reaction system: keeping other process variables constant, the strength was introduced separately. for , and The step disturbance, using X-ray diffraction measurement of layer Crystal planes and The full width at half maximum (FWHM) of a crystal plane is defined as the defect density indicator. Experimental measurements Follow The increase in the value exhibits an exponential growth trend, thus determining the controlled release rate constant under this material system. Defect density identifier Satisfies the functional relationship: ,in, The sustained release rate constant is determined by the defect density of the asymmetric lattice defects; Based on the material property coefficient and defined as ; It is the charge shielding factor and is defined as ; This is a defect density identifier; under this procedure, the disturbance intensity is set. for At that time, it was measured for Calculation Value Regarding the physical transformation mechanism of defect density indicators, in the system of this invention, the 110 crystal plane of the hydrotalcite layer reflects the transverse periodic structure inside the layer, while the 003 crystal plane reflects the axial stacked structure. When a hydrogen ion concentration step disturbance is introduced during the aging stage, the local dissolution and rearrangement of metal cations in the layer leads to lattice distortion and asymmetric defects, resulting in a significant broadening of the diffraction peak of the 110 crystal plane and a significant increase in its full width at half maximum (FWHM). Meanwhile, the integrity of the 003 crystal plane remains relatively stable. Therefore, the increase in the FWHM ratio of the 110 crystal plane to the 003 crystal plane directly corresponds to the increase in the longitudinal and transverse periodic mismatch inside the lattice. This ratio is mathematically proportional to the density of asymmetric lattice defects in the layer, and thus can be used as a reliable indicator for quantitatively characterizing defect density.

[0039] Regarding the diffusion index The control involves adjusting the cooling rate of the slurry during the later stages of aging to construct amorphous wrinkled edges; the aged slurry... Suspension slurry with The cooling rate drops to The following steps were performed, maintaining this low temperature, via silane coupling agent grafting through active hydroxyl sites; transmission electron microscopy revealed that this cooling rate resulted in a depth of [missing information - likely a specific depth] at the radial edge of the laminate. The amorphous region; the fluctuating electron cloud density within this region generates physical damping for trace element anions, and the diffusion index at this depth is measured. for Specifically, the fluctuations in electron cloud density at the microscopic level manifest as asymmetric distortions in the local electrostatic field caused by non-equilibrium atomic arrangement. These alternating fluctuations in microscopic charge distribution transform into a continuous potential gradient distribution at the mesoscopic scale by forming dense local potential barrier groups at the lattice edges. When trace element anions pass through the 38-nanometer-deep amorphous wrinkled region, they must continuously overcome the electrostatic repulsion and Coulomb resistance generated by these potential barrier groups. This microscopic-to-mesoscopic energy transfer chain macroscopically manifests as the overall superposition of mass transfer resistance, thus continuously constraining the competitive replacement rate of external anions throughout the material's service life of over 180 days. This achieves a cross-scale linear transfer of the macroscopic mass transfer damping effect from microscopic electronic structure distortion. This numerical value indicates that... to Within the range of wrinkle depth, increasing the cooling rate makes Value direction Approaching; the prepared sample group at a NaCl mass concentration of Performance verification was conducted in a high-salt liquid phase environment; service life was measured. for At that time, the cumulative release rate of trace elements The measured value is ; the interior of the particles passes through The large hole and The interconnected micropores form mass transfer channels, and the volume expansion rate of the sample group is... The above procedure achieves a mapping from synthesis parameters to release performance by converting lattice defects into quantifiable defect density identifiers.

[0040] Example 5: In a high-ammonia-nitrogen electronic industrial wastewater treatment project, there was a deviation between the background ion concentration of the influent liquid phase and the interlayer anion exchange potential. The preparation benchmark for the ZnMgAl-type layered double hydroxide functional core was determined by executing a standardized pre-calibration procedure. Metal salt raw materials were selected for pre-reaction, maintaining a zinc, magnesium, and aluminum molar ratio of 2.2:0.8:1.0. During the aging process, the change rate of electrical conductivity of the aging slurry is monitored using an online detection system. ;when When the absolute value of the hydrogen ion concentration is below 0.05 mS / cm for 15 consecutive minutes, the crystal growth enters an equilibrium state. Hydrogen ion concentration step perturbations Ip with intensities of 2.0, 2.8, and 3.5 are injected into the equilibrium system, and the defect density label Ddef corresponding to the asymmetric lattice defects generated at different intensities is recorded. The density label Ddef is then calculated using the formula... Solving for the basic material property coefficients With charge shielding factor ,in The sustained release rate constant is determined by the defect density of the asymmetric lattice defects. Based on the material property coefficients, Here, Ddef is the charge shielding factor, and Ddef is the defect density identifier. The obtained calibration parameters serve as input values ​​for adjusting the amount of hydrogen ion concentration step perturbation applied during production, ensuring that the physical binding energy of trace element anions is within the range of 20.5 kJ / mol to 45.8 kJ / mol. The values ​​of the basic material characteristic coefficient and the charge shielding factor are determined by nonlinear least squares fitting of the release rate constants of multiple samples under different hydrogen ion perturbation intensities. Specifically, the basic material characteristic coefficient reflects the benchmark value of the inherent ion exchange desorption rate of hydrotalcite-like material under a defect-free ideal state. Its upper physical limit is constrained by the maximum free diffusion rate of trace element anions between layers, and its lower limit is determined by the coulombic rate between layers. The gravitational binding energy determines the ion release rate. If it is below 0.001, it means that the framework is too strong to bind the ions, making release impossible. The charge shielding factor characterizes the contribution weight of the local electrostatic distortion caused by defects to the overall mass transfer barrier. Its value determines the response sensitivity of the rate constant as the defect density increases. When it deviates from the reasonable engineering range of 0.4 to 1.2, it will cause a systematic deviation of more than 15% between the theoretically calculated slow-release constant and the measured value. This invention collects steady-state release data of five samples with different defect densities in a constant-temperature liquid phase environment, and uses the measured release curve as a benchmark to perform exponential function fitting. Finally, the above-mentioned optimal characteristic constants are determined, thereby ensuring the accuracy of the kinetic prediction model.

[0041] When the system influent flow rate fluctuates beyond To maintain the confined release path formed by the interpenetrating network structure and the interface transition layer, kinetic compensation calibration was performed on the cooling steps in the preparation procedure. The slurry that had completed equilibrium aging was cooled through a heat exchange module, and the flow rate of the circulating cooling medium was adjusted to control the cooling rate of the slurry. exist to The temperature varies within a certain range until the slurry temperature drops to a certain level. The following particle size was selected. to Hydraulic shear failure tests were conducted on the sample group, and the interfacial peeling rate was measured as a function of... The relationship between the changes was used to determine how to reduce the interface peeling rate to below a certain level. And diffusion index In to The cooling parameters of the interval, among which The cooling rate is defined as ; where the cooling rate is set to . At this time, the edges of the amorphous wrinkles generate physical damping against molybdate ions in the radial direction of the laminate, and the volume expansion rate of the resulting composite functional particles under impact load is no higher than After pre-calibration and calibration, the sustained-release performance of the composite functional particles during service was within the error range corresponding to the preset kinetic model. To quantitatively confirm the improvement effect on interface stability, the interface peeling rate of this invention was determined and calculated using the following standardized pure digital procedure: 50 grams of dried composite functional particle sample were randomly weighed and placed into a standard cylindrical stirred reactor containing 500 ml of distilled water. A six-bladed paddle stirrer was turned on and the rotation speed was kept constant at 400 rpm. Hydraulic shearing was continuously performed for 48 hours at a temperature of 25 degrees Celsius. After shearing, the sample was filtered and separated using a standard sieve with a 1 mm aperture. The free microbial component solids lost through the sieve were collected and dried at 105 degrees Celsius to constant weight. Finally, the mass of the free microbial component obtained by drying through the sieve was divided by the estimated total mass of microbial components contained in the composite functional particles before the experiment. The resulting percentage value was defined as the interface peeling rate.

[0042] Example 6: In a large-scale preparation verification scenario, the differences in crystal water content and heat of dissolution fluctuations among different batches of industrial-grade metal salt raw materials can cause uneven lattice growth rates. An on-site optimization procedure is executed to calibrate the preparation parameters, and a control system equipped with a potential sensor monitors the slurry in the reactor. The evolution curve was obtained, and the buffer capacity of the current batch of raw materials was determined by potentiometric titration using a standard acid solution. Based on the buffer capacity, the stepping frequency of the metering pump was adjusted to control the acid pulse injection rate, so that the system... The intensity of the hydrogen ion concentration step disturbance generated internally Locked in The surface free energy at the edge of the obtained sample layer is higher than that at the center of the layer. Furthermore, the physical binding energy generated by asymmetric lattice defects is at to In the non-uniform gradient range between these regions, under this condition, the baseline measurement of the surface free energy of the central region of the ZnMgAl type hydrotalcite functional core layer is 170.2 millijoules per square meter. Based on this baseline value, the absolute surface free energy of 35.5 millijoules per square meter added at the edge of the layer corresponds to a relative increase of 20.8% higher than that of the central region, which is perfectly within the preset ratio range of 15% to 25%. By providing the inherent surface free energy of the central region as a reference benchmark, the mathematical alignment and logical closure between the absolute energy density difference and the macroscopic relative ratio boundary are achieved.

[0043] When the obtained composite functional particles are applied to environments with drastic temperature fluctuations and background ion concentrations at... Under operating conditions, to investigate the evolution of the crosslinking degree of polyvinyl alcohol (PVA) and sodium alginate in a high-salt environment, a compatibility ratio correction procedure based on the service environment baseline was implemented. Based on the measured ion shielding effect, the weight ratio of PVA to sodium alginate in the interpenetrating network structure was adjusted from... Adjusted to And in conjunction with the cooling rate, it is set as The induced amorphous wrinkles at the edges maintain the physical continuity of the confined release path, and the resulting composite functional particles are internally... The large hole and The interconnected micropores forming the mass transfer channels remain stable throughout the operating cycle, and the resulting volume expansion rate remains stable at [value missing]. And diffusion index for Actual measured cumulative release rate of trace elements Evolution numerical and relational The calculated prediction bias is lower than .

[0044] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention.

[0045] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A type of slow-release trace element-based hydrotalcite-microbial composite functional particle, characterized in that, include: Hydrotalcite-like functional core, microbial components and located in An interfacial transition layer between the hydrotalcite-like functional core and the microbial components; The molar ratio of metal cations in the hydrotalcite-like functional core satisfies for to to ; The hydrotalcite-like functional core has amorphous wrinkled edges and asymmetric lattice defects formed by the step perturbation of hydrogen ion concentration during the aging stage. The interlayer intercalation of the hydrotalcite-like functional core contains trace element anions, and the asymmetric lattice defects cause the physical binding energy between the trace element anions and the layers to exhibit [variable characteristics]. to Non-uniform gradient distribution; The microbial component includes bioactive units and an interpenetrating network structure for encapsulating the bioactive units. The interpenetrating network structure is composed of polyvinyl alcohol and sodium alginate crosslinked together. The interface transition layer is formed by a silane coupling agent. The active hydroxyl sites at the edge of the layered structure of the hydrotalcite-like functional core are grafted in situ, and the thickness of the interfacial transition layer is [missing information]. to In a liquid medium environment, the interfacial transition layer, interpenetrating network structure, and amorphous wrinkled edges together constitute a confined release pathway for trace element anions. The amorphous wrinkled edges, in particular, provide radial... to The morphology within the depth creates mass transfer resistance for ion exchange; The gradient binding energy generated by asymmetric lattice defects constrains the desorption rate of trace element anions, causing the trace element anions to be released at a uniform and slow rate throughout the material's service life.

2. The hydrotalcite-microbial composite functional particle for slow-release trace elements according to claim 1, characterized in that, During the preparation process, the hydrotalcite-like functional core... to At the aging temperature, an intensity of [value missing] is introduced into the reaction system. to The hydrogen ion concentration step perturbation induces Asymmetric lattice defects are generated inside the hydrotalcite-like material. The interlayer spacing of the hydrotalcite-like functional core is to .

3. The hydrotalcite-microbial composite functional particle for slow-release trace elements according to claim 1, characterized in that, The silane coupling agent used in the interface transition layer is The interface transition layer is in The hydrotalcite-like functional core is located at a temperature below In liquid slurry, through the active hydroxyl sites at the edge of the plate and The tortuosity of the confined release pathway generated by the dehydration condensation reaction of ethanol solution is regulated by the steric hindrance of the organic long chain of the silane coupling agent.

4. The hydrotalcite-microbial composite functional particle for slow-release trace elements according to claim 1, characterized in that, Bioactive units include denitrifying thiobacilli and denitrifying polyphosphate-accumulating bacteria; microbial components and The weight ratio of the hydrotalcite-like functional core is to The weight ratio of polyvinyl alcohol to sodium alginate in the interpenetrating network structure is: to .

5. The hydrotalcite-microbial composite functional particle for slow-release trace elements according to claim 1, characterized in that, The particle size of the composite functional particles is to It has a multi-level pore size distribution structure inside, in which The micropore size formed by the hydrotalcite-like functional core is to The large aperture formed by the interpenetrating network structure is to Micropores and macropores are interconnected to form mass transfer channels for trace element anions.

6. The hydrotalcite-microbial composite functional particle for slow-release trace elements according to claim 1, characterized in that, Cumulative release rate of trace elements in composite functional particles The following relationship must be satisfied: ,in, for Cumulative release percentage at any given time The sustained release rate constant is determined by the defect density of the asymmetric lattice defects. For the service life of materials in a liquid medium environment, Let be the diffusion exponent for releasing path constraints from the bounded domain, and satisfy to When the background ion concentration of the liquid medium environment is to At that time, the release kinetics curve of trace elements conforms to the quasi-zero-order release model controlled by energy order.

7. The hydrotalcite-microbial composite functional particle for slow-release trace elements according to claim 1, characterized in that, The crystallinity of the hydrotalcite-like functional core is to Furthermore, the surface free energy at the edges of amorphous wrinkles is higher than that of... Central area of ​​hydrotalcite-like slab to The fluctuating electron cloud density at the edges of amorphous wrinkles forms physical damping against trace element anions.

8. The hydrotalcite-microbial composite functional particle for slow-release trace elements according to claim 1, characterized in that, Trace element anions include at least one of molybdate ions, cobalt ion complex anions, or selenate ions, and these trace element anions are distributed via ion exchange. The interlayer of the hydrotalcite-like functional core, and trace element anions in The mass percentage of hydrotalcite-like functional core is to .

9. The hydrotalcite-microbial composite functional particle for slow-release trace elements according to claim 1, characterized in that, The surface negative charge density of the hydrotalcite-like functional core is determined by the molar ratio. and Adjustment of the ratio; when molar ratio in to When fluctuating within a range, The electrostatic affinity between the hydrotalcite-like functional core and the microbial components changes accordingly to maintain the microbial components at a liquid flow rate lower than [a certain value]. The interface stability during the process, and the uniform slow release period of trace elements is not less than During the material's service life, the volume expansion rate of the composite functional particles is lower than that of the composite functional particles. Used to maintain interface transition layers, interpenetrating network structures and Mechanical anchoring force between the functional cores of hydrotalcite-like materials.

10. The application of a slow-release trace element-based hydrotalcite-microbial composite functional particle, characterized in that, The hydrotalcite-microbial composite functional particles of the slow-release trace elements described in claim 1 are used as a slow-release trace element additive in a liquid matrix environment.

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