Multi-stage water treatment process for pet water purification

Abstract

The present application relates to water treatment process technical field, disclose a kind of multistage water treatment process for pet drinking water purification, comprising: control the circulating fluid to be treated sequentially through tertiary amine functional group modified porous substrate bed layer and carry out charge destabilization coagulation interception, through the micro area potential difference generated by the hetero transition metal composite particle layer consisting of active copper particles and active zinc particles mixed protein spatial conformation disassembly denaturation inactivation, and when the bed layer layer resistance pressure drop rises to calibration threshold, trigger fluid circulation power unit to adjust output power, to increase fluid linear velocity in situ crystal nucleus high shear scouring stripping, finally introduce the porous carbon composite adsorption unit of specific micropore pore size and specific surface area, the present application is aimed at specific protein molecule solid-liquid interface crosslinking behavior carries out charge and time sequence flow field reconstruction, from the path of blocking bacterial biofilm attachment film formation within the physicochemical reaction procedure, effectively maintain the dynamic water flux retention rate of filtration system under the state of continuous load accumulation.

Description

Technical Field

[0001] This invention relates to a multi-stage water treatment process for purifying drinking water for pets, belonging to the field of water treatment technology. Background Technology

[0002] Currently, in fluid purification processes, a cascaded combination of porous media retention, surface adsorption, and electrochemical degradation of metal matrices is the mainstream approach for stabilizing flow turbidity, reducing total organic carbon concentration in water, and delaying macromolecular cross-linking and aggregation. This process involves the fluid alternately passing through layers of materials with specific spatial characteristics, utilizing the physicochemical properties of the media surface to retain suspended solids and dissolved macromolecules. A fixed physical and chemical field is established at the solid-solid interface, and the positive charge on the modified material surface adsorbs and enriches negatively charged flowing colloids, thereby reducing the degree of freedom of movement of colloidal particles in the fluid. Simultaneously, a local closed galvanic cell is constructed through the contact of heterogeneous metal particles with potential differences. When proteins carrying cross-linked spatial conformations cross the local potential field between adjacent particles, the disulfide bonds maintaining the folded shape within the molecule undergo spontaneous electron transfer and break, leading to the disintegration of the protein's higher-order conformation and loss of interfacial cross-linking activity.

[0003] Optimizing the microstructure or particle size distribution of fillers to delay particle caking has limitations without the support of flow field regulation and control methods. For example, Chinese invention patent application CN106865697A discloses a copper-zinc alloy particle for water purification, its preparation method, and a water purification filter media. This method utilizes a combination of alloy particles with different specific particle size ratios to reduce the contact area between particles and decrease the probability of physical caking. However, this static particle size distribution relies on a low organic load fluid environment. In pet drinking water, where high-viscosity salivary proteins and inorganic salt hardness components coexist, the lack of a dynamic flow field for transient hydraulic shearing at the solid-liquid interface allows nascent crystal nuclei to easily cross-link with protein gels in situ, solidifying into a dense scale layer between metal particles. This irreversibly masks electrochemical active sites, causing the loss of the local reduction potential difference in the galvanic cell. However, when high-viscosity proteins are continuously introduced into the circulation system along with high concentrations of inorganic salt hardness components, existing cascaded combined processes will reveal defects such as interfacial fouling and site masking failure. A large number of macromolecular colloids enriched at the solid-liquid interface will accumulate disorderly on the surface and cross-link and solidify into a dense gel layer. This not only causes the flow flux of the medium to decrease monotonically, but also induces inorganic scaling on the surface of metal particles. The resulting composite impedance scale layer completely cuts off the electron transfer path between adjacent particles, causing the loss of the local reduction potential difference of the galvanic cell. To suppress this kind of solid-liquid interface physicochemical degradation, linear improvement measures such as increasing the filling volume or maintaining a high linear velocity constant flow field are adopted. However, this will not only compress the hydraulic residence time of the fluid in the charge balance region, making it lower than the reaction kinetic limit of electrostatic destabilization and coagulation, but also cause a surge in distribution pressure drop due to the accumulation of filter bed resistance.

[0004] Therefore, the technical problem to be solved by this invention is how to adaptively switch the non-uniform pulse shear flow field according to the pressure drop fluctuation feedback of the flow interface, so as to break the cross-linking of macromolecular gel at the solid-liquid interface and peel off the primary crystal nuclei in situ without the addition of chemical additives. Summary of the Invention

[0005] To address the problems in the background art, the technical solution of the present invention is as follows: A multi-stage water treatment process for purifying pet drinking water, comprising the following steps:

[0006] Step S1: Control the circulating fluid to be treated to pass through the tertiary amine functional group modified porous matrix bed at an initial linear velocity of 0.05 m / s to 0.12 m / s, and control the hydraulic residence time of the circulating fluid to be treated in the tertiary amine functional group modified porous matrix bed to be 1.5 s to 3.0 s.

[0007] Step S2: The circulating fluid to be treated after being modified by the tertiary amine functional group into the heterogeneous transition metal composite particle layer is introduced into the heterogeneous transition metal composite particle layer. The heterogeneous transition metal composite particle layer is composed of active copper particles with a particle size of 0.5 mm to 1.2 mm and active zinc particles with a particle size of 0.5 mm to 1.2 mm in a mass ratio of 1:2.5 to 1:4.0.

[0008] Step S3: By adjusting the output power of the fluid circulation power unit, the linear velocity of the circulating fluid to be processed in the heterogeneous transition metal composite particle layer is increased stepwise from the initial linear velocity to 0.6 m / s to 1.5 m / s, and the duration of each stepwise increase is 3 s to 10 s.

[0009] Step S4: The circulating fluid to be treated after passing through the heterogeneous transition metal composite particle layer is introduced into a porous carbon composite adsorption unit with an average micropore diameter of 1.5 nm to 4.5 nm and a specific surface area of ​​800 m² / g to 1300 m² / g, and the flow rate of the circulating fluid to be treated in the porous carbon composite adsorption unit is controlled to be 0.02 m / s to 0.08 m / s.

[0010] Preferably, under the conditions of the initial linear velocity controlled in step S1 and the mass ratio configured in step S2, the density of tertiary amine functional groups on the surface of the tertiary amine functional group modified porous matrix bed is 0.45 mmol / g to 0.85 mmol / g, the packing density of the tertiary amine functional group modified porous matrix bed is 0.62 g / cm³ to 0.78 g / cm³, and the average pore size is 10 μm to 35 μm; in step S2, the purity of the active copper particles is not less than 99.9%, the purity of the active zinc particles is not less than 99.9%, and the surface roughness of the active copper particles and active zinc particles in the heterogeneous transition metal composite particle layer is... The range is from 0.8 μm to 2.5 μm.

[0011] Preferably, for the control of fluid linear velocity in step S3, step S3 includes the following refined sub-steps: Step S31, the conductivity fluctuation rate and layer resistance pressure drop parameters of the circulating fluid to be processed are collected by the fluid parameter acquisition unit; Step S32, when the conductivity fluctuation rate continuously exceeds 1.5% within 120s and the layer resistance pressure drop parameter exceeds the calibrated resistance threshold of 0.02MPa, it is determined that the surface of the heterogeneous transition metal composite particle layer has reached the upper limit of scaling resistance and a power adjustment trigger signal is issued; Step S33, in response to the power adjustment trigger signal, the driving frequency of the fluid circulation power unit is adjusted so that the output power of the fluid circulation power unit is increased from the reference power to the excitation power within 1.5s, and the fluid linear velocity is increased to the numerical range of the step acceleration rate.

[0012] Preferably, the tertiary amine functional group modified porous matrix bed introduced in step S1 is prepared by the following refined sub-steps: Step S11, porous aluminosilicate ceramic particles are immersed in a 3% to 8% (w / w) 3-aminopropyltriethoxysilane ethanol solution and reacted at a constant temperature of 50°C to 65°C for 2 to 4 hours to complete silanization, and then filtered and dried to obtain a solid intermediate; Step S12, the solid intermediate is introduced into a mixed reaction system of formaldehyde and formic acid and reacted at a constant temperature of 80°C to 95°C for 4 to 8 hours to complete methylation, so that tertiary amine functional groups are grafted onto the surface of the porous aluminosilicate ceramic particles, and then filtered, washed and dried to obtain a tertiary amine functional group modified porous matrix bed.

[0013] Preferably, in step S4, when the porous carbon composite adsorption unit intercepts small molecule denatured products, the porous carbon composite adsorption unit is composed of activated coconut shell activated carbon and bone char mixed in a mass ratio of 2:1 to 5:1. The total pore volume of the porous carbon composite adsorption unit is 0.65 cm³ / g to 0.92 cm³ / g, and the proportion of micropores with a pore size of less than 2 nm to the total pore volume is 75% to 88%.

[0014] Preferably, in step S1, the protein concentration in the circulating fluid to be treated is between 15 mg / L and 85 mg / L, and after step S1, the retention rate of macromolecular organic matter in the circulating fluid to be treated is not less than 92%.

[0015] Preferably, in step S2, the particle size of the active copper particles is 0.6 mm to 1.0 mm, the particle size of the active zinc particles is 0.6 mm to 1.0 mm, and the filling height of the heterogeneous transition metal composite particle layer composed of the mixture of active copper particles and active zinc particles is 60 mm to 120 mm.

[0016] Preferably, in step S3, under the shear condition where the fluid linear velocity increases by a step, the transient shear stress generated inside the heterogeneous transition metal composite particle layer is controlled to be between 1.2 Pa and 3.8 Pa. The transient shear stress cleans the contact interface between the active copper particles and the active zinc particles to reduce the fluid flow resistance.

[0017] Preferably, in step S4, the circulating fluid to be treated passes through the drainage branch path after the porous carbon composite adsorption unit, so that the hydraulic residence time of the circulating fluid to be treated in the porous carbon composite adsorption unit is stabilized within the range of 2.0s to 5.0s, and the circulating fluid to be treated is introduced into the light-proof and sealed material flow channel.

[0018] Compared with the prior art, the beneficial effects of the present invention are:

[0019] 1. In multi-stage water treatment for pet drinking water purification, a modified porous matrix bed with a specific positive potential adsorbs negatively charged colloidal proteins. Within a limited hydraulic residence time, the charge state at the solid-liquid interface is regulated to achieve pre-interception of macromolecules, slowing down the disordered deposition rate of organic matter on the medium surface. Together with the subsequent heterogeneous transition metal composite particle layer, the electrochemical denaturation effect generated by the spontaneous local micro-region redox potential difference breaks the disulfide bonds in the residual protein space maintenance structure, denatures and deactivates them, and reduces the interfacial adhesion strength of the amorphous gel fouling layer. This maintains the dynamic water flux retention rate of the filtration system under continuous load accumulation, and slows down the rate of increase in system hydraulic resistance caused by irreversible organic fouling.

[0020] 2. This process utilizes a differential pressure sensor to collect the transient pressure drop rate at the end of the heterogeneous transition metal composite particle layer in real time. During the nucleation critical period when inorganic salts and viscous proteins accumulate at the inlet water, causing a phase change, the fluid linear velocity is increased by a step increase in a short time by dynamically adjusting the output power of the distribution pump. The abrupt hydraulic shear stress generated by the non-uniform transient flow field is used to strip the amorphous calcium carbonate nuclei accumulated at the particle contact interface, preventing scale products from solidifying into a dense scale layer under high hardness and complex water quality conditions. This avoids the electrochemical sites on the surface of active metal particles being masked and passivated by the scale layer, thereby ensuring the long-term stability and activity of the electron transfer path of the spontaneous micro-cell.

[0021] 3. This process constructs numerous microscopic galvanic cells in situ under a conductive medium by using active copper and zinc particles in a limited mass ratio. Due to the boundary constraint of the dynamic pressure drop on the fluid shear collision frequency, the spontaneous local micro-region redox potential difference formed between adjacent particles causes spontaneous electron transfer in the residual salivary proteins in the fluid. This forcibly breaks down the key disulfide bonds that maintain the higher-order spatial structure, reduces the tertiary conformational integrity of the protein molecules, and destroys the basic matrix environment for bacterial attachment and secretion of extracellular polymers in the water. In this way, the solid-liquid interface attachment and film formation pathway of bacterial biofilm is blocked from the physicochemical reaction process, effectively preventing the system from releasing specific volatile odor molecules due to biofilm growth. Attached Figure Description

[0022] Figure 1 This is a flowchart of the multi-stage water treatment process of the present invention, which includes charge destabilization and step acceleration control.

[0023] Figure 2 This is a diagram showing the connection relationship of the multi-stage water treatment unit for fluid parameter feedback regulation according to the present invention.

[0024] The objectives, features, and advantages of this invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0025] The technical solutions of the embodiments of this application will be clearly described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this application are within the scope of protection of this application.

[0026] A multi-stage water treatment process for purifying pet drinking water includes the following steps:

[0027] Step S1: Control the circulating fluid to be treated to pass through the tertiary amine functional group modified porous matrix bed at an initial linear velocity of 0.05 m / s to 0.12 m / s, and control the hydraulic residence time of the circulating fluid to be treated in the tertiary amine functional group modified porous matrix bed to be 1.5 s to 3.0 s.

[0028] Step S2: The circulating fluid to be treated after being modified by the tertiary amine functional group into the heterogeneous transition metal composite particle layer is introduced into the heterogeneous transition metal composite particle layer. The heterogeneous transition metal composite particle layer is composed of active copper particles with a particle size of 0.5 mm to 1.2 mm and active zinc particles with a particle size of 0.5 mm to 1.2 mm in a mass ratio of 1:2.5 to 1:4.0.

[0029] Step S3: By adjusting the output power of the fluid circulation power unit, the linear velocity of the circulating fluid to be processed in the heterogeneous transition metal composite particle layer is increased stepwise from the initial linear velocity to 0.6 m / s to 1.5 m / s, and the duration of each stepwise increase is 3 s to 10 s.

[0030] Step S4: The circulating fluid to be treated after passing through the heterogeneous transition metal composite particle layer is introduced into a porous carbon composite adsorption unit with an average micropore diameter of 1.5 nm to 4.5 nm and a specific surface area of ​​800 m² / g to 1300 m² / g, and the flow rate of the circulating fluid to be treated in the porous carbon composite adsorption unit is controlled to be 0.02 m / s to 0.08 m / s.

[0031] Preferably, under the conditions of the initial linear velocity controlled in step S1 and the mass ratio configured in step S2, the density of tertiary amine functional groups on the surface of the tertiary amine functional group modified porous matrix bed is 0.45 mmol / g to 0.85 mmol / g, the packing density of the tertiary amine functional group modified porous matrix bed is 0.62 g / cm³ to 0.78 g / cm³, and the average pore size is 10 μm to 35 μm; in step S2, the purity of the active copper particles is not less than 99.9%, the purity of the active zinc particles is not less than 99.9%, and the surface roughness of the active copper particles and active zinc particles in the heterogeneous transition metal composite particle layer is... The range is from 0.8 μm to 2.5 μm.

[0032] Preferably, for the control of fluid linear velocity in step S3, step S3 includes the following refined sub-steps: Step S31, the conductivity fluctuation rate and layer resistance pressure drop parameters of the circulating fluid to be processed are collected by the fluid parameter acquisition unit; Step S32, when the conductivity fluctuation rate continuously exceeds 1.5% within 120s and the layer resistance pressure drop parameter exceeds the calibrated resistance threshold of 0.02MPa, it is determined that the surface of the heterogeneous transition metal composite particle layer has reached the upper limit of scaling resistance and a power adjustment trigger signal is issued; Step S33, in response to the power adjustment trigger signal, the driving frequency of the fluid circulation power unit is adjusted so that the output power of the fluid circulation power unit is increased from the reference power to the excitation power within 1.5s, and the fluid linear velocity is increased to the numerical range of the step acceleration rate.

[0033] Preferably, the tertiary amine functional group modified porous matrix bed introduced in step S1 is prepared by the following refined sub-steps: Step S11, porous aluminosilicate ceramic particles are immersed in a 3% to 8% (w / w) 3-aminopropyltriethoxysilane ethanol solution and reacted at a constant temperature of 50°C to 65°C for 2 to 4 hours to complete silanization, and then filtered and dried to obtain a solid intermediate; Step S12, the solid intermediate is introduced into a mixed reaction system of formaldehyde and formic acid and reacted at a constant temperature of 80°C to 95°C for 4 to 8 hours to complete methylation, so that tertiary amine functional groups are grafted onto the surface of the porous aluminosilicate ceramic particles, and then filtered, washed and dried to obtain a tertiary amine functional group modified porous matrix bed.

[0034] Preferably, in step S4, when the porous carbon composite adsorption unit intercepts small molecule denatured products, the porous carbon composite adsorption unit is composed of activated coconut shell activated carbon and bone char mixed in a mass ratio of 2:1 to 5:1. The total pore volume of the porous carbon composite adsorption unit is 0.65 cm³ / g to 0.92 cm³ / g, and the proportion of micropores with a pore size of less than 2 nm to the total pore volume is 75% to 88%.

[0035] Preferably, in step S1, the protein concentration in the circulating fluid to be treated is between 15 mg / L and 85 mg / L, and after step S1, the retention rate of macromolecular organic matter in the circulating fluid to be treated is not less than 92%.

[0036] Preferably, in step S2, the particle size of the active copper particles is 0.6 mm to 1.0 mm, the particle size of the active zinc particles is 0.6 mm to 1.0 mm, and the filling height of the heterogeneous transition metal composite particle layer composed of the mixture of active copper particles and active zinc particles is 60 mm to 120 mm.

[0037] Preferably, in step S3, under the shear condition where the fluid linear velocity increases by a step, the transient shear stress generated inside the heterogeneous transition metal composite particle layer is controlled to be between 1.2 Pa and 3.8 Pa. The transient shear stress cleans the contact interface between the active copper particles and the active zinc particles to reduce the fluid flow resistance.

[0038] Preferably, in step S4, the circulating fluid to be treated passes through the drainage branch path after the porous carbon composite adsorption unit, so that the hydraulic residence time of the circulating fluid to be treated in the porous carbon composite adsorption unit is stabilized within the range of 2.0s to 5.0s, and the circulating fluid to be treated is introduced into the light-proof and sealed material flow channel.

[0039] Example 1: In an application scenario where circulating water flows through a porous matrix bed modified with tertiary amine functional groups, the initial protein concentration of the circulating fluid to be treated is 45 mg / L, the initial turbidity is 3.2 NTU, and the initial total organic carbon is 18.4 mg / L. The porous matrix bed modified with tertiary amine functional groups is composed of silica gel particles with a particle size of 0.5 mm. The tertiary amine functional groups on the surface of these silica gel particles provide positive charge sites. The measured surface... With a potential of +32mV, the fluid circulation power unit controls the circulating fluid to pass through the tertiary amine functional group modified porous matrix bed at an initial linear velocity of 0.08m / s, so that the hydraulic residence time of the circulating fluid in it is maintained at 2.1s. When the negatively charged salivary protein colloid passes through the tertiary amine functional group modified porous matrix bed, it undergoes electrostatic neutralization and pre-coagulation with the tertiary amine functional groups on the surface, thereby achieving pre-interception of macromolecular organic matter.

[0040] The pretreated circulating fluid is introduced into a heterogeneous transition metal composite particle layer, which is composed of active copper particles and active zinc particles mixed at a mass ratio of 1:3.2, with a particle size of 40 to 60 mesh and a packing height of 85 mm. Due to the presence of an oxide film on the particle surface, a spontaneous localized micro-region redox potential difference of 0.31 V is formed between adjacent metal particles. Specifically, at the contact boundary between the active copper and active zinc particles, a localized high-intensity electric field gradient is formed due to the microscopic protrusion structure with a surface roughness Ra of 0.8 μm to 2.5 μm. When negatively charged salivary protein molecules are adsorbed due to the pre-condensation, and... When the protein molecule adheres closely to the solid contact interface at the contact boundary, the three-dimensional spatial conformation of the protein molecule undergoes orientation polarization distortion. The deeply buried covalent disulfide bonds are exposed and adjacent to the electron transfer path of the local micro-region galvanic cell. Thus, under the synergistic effect of the applied electric field gradient catalysis and proton coupling electron transfer, the activation energy barrier for the breaking of covalent disulfide bonds is reduced to the electrochemical reaction kinetic range that can be crossed by the local micro-region potential difference of 0.31V. Spontaneous electron transfer and dissociation of disulfide bonds are achieved within a hydraulic residence time of 2.1s. When the circulating fluid flows through this particle layer, the protein molecule undergoes electron transfer under the action of the potential gradient, the disulfide bonds in the spatial conformation break, and the protein denatures and becomes inactive.

[0041] When the fluid circulation power unit detects an increase in the rate of change of transient pressure drop at the end of the heterogeneous transition metal composite particle layer, and the transient pressure drop changes from the initial pressure drop... The step increase rises to the detection threshold of 1.65. At that time, the fluid circulation power unit triggers and adjusts its output power, increasing the linear velocity of the circulating fluid from 0.08 m / s to 0.45 m / s within 5 seconds. This velocity is maintained for 18 seconds to utilize transient hydraulic shear stress to peel off the primary calcium carbonate crystal nuclei on the surface of the metal particles. The fluid circulation power unit then increases its output power, causing the linear velocity of the heterogeneous transition metal composite particle layer to increase from the initial linear velocity to 1.2 m / s and maintain this velocity for 6 seconds. When the surface of the heterogeneous transition metal composite particle layer reaches the upper limit of scaling resistance, the primary crystal nuclei precipitate and detach at the particle contact interface. The localized charge distribution in the particle layer generates high-frequency disturbances. When the conductivity fluctuation rate continuously exceeds 1.5% within 120 seconds and the layer resistance pressure drop parameter exceeds 0.02 MPa, a flushing operation is triggered. The fluid parameter acquisition unit includes two sets of miniature conductivity sensors and differential pressure transmitters integrated in series at the inlet and outlet of the heterogeneous transition metal composite particle layer. The analog signal output of each sensor is connected to the analog-to-digital converter input interface of the control chip via shielded wires. The control chip performs a moving average variance calculation on the acquired conductivity data with a time window of 120 seconds to obtain the conductivity fluctuation rate. The specific closed-loop calculation process of conversion and dimension elimination is as follows: the control chip continuously reads the analog voltage output from the two sets of miniature conductivity sensors at a discrete sampling frequency of 50Hz and converts it into real-time conductivity values. Within the 120-second time window, 6000 discrete sample points are cyclically latched and the moving average variance value is calculated. At this time, the physical dimension of the variance value is square microsieverts. The control chip then divides the moving average variance value directly by the square of the moving average of 6000 sample points within the time window. This direct division of the numerator and denominator, with the same physical dimensions, achieves complete dimensional offsetting. Finally, the dimensionless ratio obtained from the division is multiplied by the pure number 100, mapping it to a dimensionless percentage value as the final conductivity fluctuation rate. This completes the closed-loop neutralization and resolution of dimensional breakage. When the trigger condition is met, the control chip outputs a pulse width modulation signal to the frequency converter drive circuit of the fluid circulation power unit. By changing the switching frequency of the inverter bridge, the operating frequency of the drive motor is instantaneously stepped from the base operating condition of 50Hz to the excitation frequency of 75Hz. The excitation power mentioned here does not depend on... Relying on any external mechanical or electromagnetic forced vibration mechanism, its hardware entity is the instantaneous electrical power output state achieved by the drive motor of the circulating pump when the windings are fully loaded within the rated output torque boundary under the 75Hz high-frequency drive current output by the frequency converter driver. In this way, the output power of the pumping motor is directly adjusted to the excitation power. The technical entity of this excitation power is the instantaneous active power achieved by the internal windings of the AC frequency converter drive motor with a rated voltage of 220V under the 75Hz high-frequency current output by the frequency converter. The frequency converter receives the pulse width modulation signal output by the control chip and changes the conduction frequency of the inverter bridge, so that the active power of the motor is instantly increased from 35W under the reference condition to 85W under the rated full-load condition, and the normal output is 1 to the impeller.Five times the overload pumping drive torque is directly converted into fluid kinetic energy without the need for mechanical or electromagnetic forced physical vibration units. This allows for precise control of the fluid linear velocity to enter the step acceleration range. After flushing, the fluid circulation power unit adjusts the flow rate back to 0.08 m / s.

[0042] Finally, the circulating fluid enters the micropores with a pore size of 3.1 nm and a specific surface area of ​​1020. The porous carbon composite adsorption unit, with a circulating fluid flow rate controlled at 85 mL / min, removes residual small-molecule denatured products and detached debris from the water through micropore sieving and surface energy adsorption. After 144 hours of operation, the results showed that the residual protein concentration in the fluid decreased to 2.4 mg / L, total organic carbon decreased to 1.9 mg / L, water turbidity was 0.18 NTU, the total system pressure drop remained at 8.2 kPa, and the number of viable bacteria in the biofilm on the media surface was [missing data]. CFU / Through a cascade of charge destabilization, electrochemical denaturation, and transient hydraulic shear stripping, the pathways for protein gel fouling and microbial film formation are blocked, maintaining the dynamic water flux of the system under continuous load accumulation.

[0043] Example 2: To verify the effectiveness of the technical solution of the present invention under different water quality loads, a water circulation purification test platform was constructed. The test environment simulated the drinking conditions of pets fed a high-protein diet. Protein solution was added to the circulating fluid at a constant rate, and the influent protein concentration was set to 25 mg / L, 45 mg / L, and 65 mg / L, respectively. The test platform was equipped with a circulation pump, a heterogeneous transition metal composite particle layer, a flow rate adjustment module, and a multi-parameter water quality monitoring component. The monitoring component has a flow rate resolution accuracy of 0.001 m / s and a pressure measurement accuracy of 0.1 kPa. In this example, the experiment was divided into the present invention test group and two control groups. Control group A removed the heterogeneous transition metal composite particle layer and retained only the porous matrix bed. Control group B adjusted the mass ratio of active copper particles to active zinc particles to 1:1.5, which exceeded the range of 1:2.5 to 1:4.0 limited by the present invention. All test groups were operated at an initial linear velocity of 0.08 m / s, and the flux decay of the filtration unit and the effluent turbidity were monitored in real time.

[0044] Under standard load conditions, after 144 hours of operation, the residual protein concentration in the fluid decreased from the initial 45 mg / L to 2.4 mg / L, total organic carbon decreased to 1.9 mg / L, water turbidity was 0.18 NTU, and the number of viable bacteria in the biofilm on the media surface was [missing information]. CFU / In control group A, due to the lack of protein denaturation caused by electron transfer, the thickness of the gel layer formed on the medium surface expanded from the initial 15 μm to 120 μm after 72 hours of operation, and the system flux decreased to 45% of the initial value. In control group B, after 96 hours of operation, the number of viable bacteria per unit area of ​​biofilm was two orders of magnitude higher than that of the experimental group of this invention, and the measured local potential difference was only 0.18 V. The reduced efficiency of protein higher-order structure breakage led to the rapid accumulation of residual organic matter on the surface of the active medium. In an optional embodiment, when the transient voltage drop rate reaches the initial voltage drop... When the stress is 1.65 times that of the crystal nucleus, the resulting hydraulic shear stress can overcome the van der Waals forces between the crystal nucleus and the metal particles, achieving efficient peeling. If the peeling threshold is set to... Excessive stripping frequency leads to increased system energy consumption, and the initial crystal nuclei on the metal surface do not reach a solidification level, resulting in a loose stripping product; if set to... The crystal nuclei on the metal surface have undergone irreversible densification, and even increasing the linear velocity to 0.60 m / s cannot achieve complete stripping. Experimental data show that within a mass ratio range of 1:2.5 to 1:4.0, the potential gradient formed between metal particles synergistically promotes the breaking of protein disulfide bonds. This process, through the coupling of electrochemical denaturation and transient hydraulic shear, has achieved long-term flux retention when dealing with different protein loads. When the load is increased from 25 mg / L to 65 mg / L, the flux retention rate of the system steadily decreases from 92.5% to 88.2%, demonstrating the adaptability of this technical solution to water quality fluctuations under long-term operation.

[0045] Example 3: In a circulating purification system used in high-frequency drinking water scenarios for multiple pets, the circulating fluid is prone to the formation of microbial biofilms on the inner wall of the pipes due to prolonged operation or ambient water temperature rising above 28°C. Furthermore, the electrochemical activity of the heterogeneous transition metal composite particles becomes passivated. To ensure treatment efficiency, the control system executes a potential reconstruction procedure based on a time decay factor before the circulating fluid enters the heterogeneous transition metal composite particle layer. When the circulating fluid passes through the heterogeneous transition metal composite particle layer, an electrochemical potential difference is formed between the active copper particles and the active zinc particles. With running time It exhibits an exponential decay trend, specifically the following relationship: ,in, The initial local potential difference is set to 0.31V; The time decay constant has a value of 0.00015. , The control unit monitors the cumulative running time of the cyclic system in real time. When the calculated potential difference When the pressure drops below the preset critical repair threshold of 0.25V, the control unit triggers the circulating distribution pump to execute a pressure pulse flushing program. This program uses the fluid circulation power unit to increase the pipeline pressure from 8.2kPa to 15.0kPa within 10s and then decrease the pressure to 5.0kPa within 0.5s. This pressure increase and decrease process is repeated 3 times. By utilizing the transient hydraulic shear force generated by the sudden change in fluid flow rate, the oxide film and calcium carbonate deposit layer formed on the surface of the metal particles are peeled off. After peeling, the effective electrochemical activity on the surface of the heterogeneous transition metal composite particles is restored, and the measured local potential difference rises back to 0.29V.

[0046] For resource allocation across multiple processing units, the control unit bases its allocation on the real-time voltage drop gradient of each processing unit. Dynamically adjust the fluid flux and set the total processing workload as follows: , No. throughput allocation ratio per processing unit Determined according to the following formula: The processing throughput of each of the aforementioned processing units is calculated as follows: , For the first Real-time voltage drop gradient of each processing unit For all within the circulatory system The system calculates the maximum flow rate for each treatment unit based on the sum of the pressure drop gradients of all treatment units, ensuring that if local fouling occurs in any unit causing an increase in the pressure drop gradient, the remaining units automatically take over the throughput, maintaining a stable total system throughput. Data after 3000 hours of continuous operation shows that the effluent protein concentration remains at 2.8 mg / L, and the number of viable bacteria in the biofilm on the media surface is [data missing]. CFU / By using potential decay compensation and adaptive allocation based on voltage drop gradient, the degradation of processing performance during long-term operation is eliminated, ensuring continuous purification effect under different biological loads.

[0047] Example 4: Before deploying the multi-pet circulating drinking water system to the field environment, an initial baseline calibration is performed to address the impact of differences in raw water mineral hardness and conductivity in different regions on the electrochemical treatment unit, and to control the initial micro-area redox potential difference of the heterogeneous transition metal composite particle layer. Calibration is performed automatically by the system: the circulating fluid... The reference linear velocity flows through the heterogeneous transition metal composite particle layer, and the control unit synchronously acquires the static potential signals at both ends of the particle layer. ,Will Record the initial reference potential difference under the current circulating water quality. This calibration value serves as the basis for zero-point calibration of subsequent dynamic potential compensation.

[0048] To ensure parameter stability during long-term operation, the system establishes an adaptive correction model for the transient pressure drop rate. This correction model is based on a preset pressure response threshold. The system updates parameters and records the circulating fluid velocity in real time. from Upgraded to During the process, the characteristics of the change in current inside the fluid circulation power unit are analyzed, and the rate of change of this current is calculated. ,in, For the current increment of the circulating fluid dynamic unit, For the flow rate adjustment time, if detected When the operating condition deviates continuously from the standard operating range, the control system automatically corrects the trigger threshold. The corrected logic is as follows: ,in, The original pressure response threshold. The corrected pressure response threshold. The current variation is based on a preset standard operating condition. The rate of change of the monitored current. To compensate for the sensitivity coefficient, this correction mechanism ensures that the fluid circulation power unit maintains consistent stripping performance under different media loads and ambient temperatures, avoiding the failure of hydraulic stripping parameters due to equipment wear or changes in water viscosity. To eliminate resistance interference caused by mechanical wear and shaft friction, the system is equipped with a current sensor with a measurement accuracy better than 0.01A and a sampling frequency of 50Hz. Before correcting the trigger threshold, the control unit controls the water circuit to switch to the no-load bypass pipeline to collect and store the motor no-load base current at the current speed. During operation calculations, the total operating current is subtracted from the no-load base current to obtain the fluid resistance current increment. A low-pass filter algorithm with a cutoff frequency of 5Hz is used to filter out high-frequency power grid noise and decouple fluid resistance variables from mechanical friction losses. The uncorrected pressure response threshold ranges from 0.01 to 0.05 MPa. The corrected pressure response threshold is greater than 0. This is the reference constant for standard operating current variation, with a value of 0.5 amperes per second. The real-time current change rate ranges from 0 to 2.5 amperes per second. The pressure compensation sensitivity coefficient is a dimensionless constant ranging from 0.1 to 0.3. (Calculated value) As the reference for the comparator inside the control unit, when the output voltage signal of the layer resistance pressure drop sensor reaches the corresponding pressure value, the control unit outputs a high-level signal to start the variable speed flushing. Furthermore, the unloaded bypass pipeline is physically connected in parallel to both ends of the multi-stage water treatment unit in the main circulating water circuit. Its inlet and outlet ends are connected to the main circulating water circuit through tee connectors. A first solenoid valve and a second solenoid valve are respectively installed on the inlet pipe section of the main circulating water circuit entering the multi-stage water treatment unit and the inlet pipe section of the unloaded bypass pipeline. The control coils of the first and second solenoid valves are electrically connected to the switch output interface of the control unit. When the unloaded bypass pipeline is switched on, the control unit drives the first solenoid valve to close and simultaneously drives the second solenoid valve to open, so that the circulating fluid completely bypasses the high-resistance porous bed and particle layer and flows only in the unloaded bypass channel, thereby ensuring that the current value collected by the current sensor is entirely composed of the inherent mechanical wear of the motor and the friction loss of the shaft.

[0049] Example 5: Before deploying pet recirculating drinking water equipment, an initial operating benchmark library adapted to local water quality parameters needs to be built through an offline calibration program. The calibration program injects mineral hardness into the test flow path. Raw water concentrations of 100 mg / L, 250 mg / L, and 400 mg / L were used, and the fluid circulation power unit was adjusted to adjust the linear velocity of the circulating fluid. The pressure drop increments at both ends of the porous matrix bed are collected within the range of 0.05 m / s to 0.12 m / s. Based on measured data, a model was fitted to fit the relationship between pressure drop increment and raw water hardness and linear velocity. ,in, To establish the characteristic function based on experimental data, calculate the gradient gain coefficient of each processing unit. Based on this, the pressure pulse trigger threshold of the circulating distribution pump under different water quality loads was determined. The relationship model, based on the Darcy-Wiesbach fluid resistance correction model, characterizes the relationship between the pressure drop of the porous media layer and the fluid velocity and inorganic salt hardness precipitation. The characteristic function... Expressed as a linear polynomial structure: ,in, This represents the pressure drop increment across the porous matrix bed, ranging from 0 to 15 kPa. The mineral hardness of raw water ranges from 100 to 400 mg / L. The linear velocity of the circulating fluid ranges from 0.05 to 0.12 meters per second. The first flow resistance coefficient, determined by the bed pore structure, ranges from 0.002 to 0.005. The second flow resistance coefficient, determined by fluid inertial drag and ranging from 15 to 25, is used to calculate the gradient gain coefficient. Subsequently, the control unit directly reads the device's cumulative operating hours output by the internal digital hardware timer and triggers the parameter update logic with a fixed calculation step size of 24 hours. Based on the current cumulative operating hours, the control unit retrieves the corresponding deterministic decay ratio constant from the pre-stored discrete step correction table in the non-volatile memory. When the cumulative operating hours are in the range of 0 to 500 hours, this ratio constant is fixed at 0.98; when it is in the range of 500 hours to 1000 hours, this ratio constant is fixed at 0.95. The control unit then controls the central processing unit to calculate the gradient gain coefficient. A pure digital product operation is performed with the extracted deterministic discrete proportionality constant, and the calculated product value is directly overwritten into the pressure response threshold register address in memory as the final correction update value. This achieves white-box adaptive dynamic update of the reference pressure pulse threshold. In this process, the value ranges of the first flow resistance coefficient A and the second flow resistance coefficient B are determined by conducting multi-component gradient flow velocity tests using a porous aluminosilicate ceramic particle bed with known porosity under standard operating conditions, and by performing polynomial regression fitting on the measured pressure drop data using the least squares method; the time decay constant... The values ​​were calculated by measuring the surface potential decay kinetics curve of the local micro-region galvanic cell after continuous operation for 1000 hours in a simulated high-frequency drinking environment for multiple pets. The 1.5% conductivity fluctuation threshold corresponds to the electrochemical abrupt change critical point at which inorganic salt primary crystal nuclei begin to spontaneously nucleate and aggregate on the surface of metal particles, triggering transient reconstruction of the double layer. When the threshold is below 1.5%, the system is in a stable operating state, and when it is above 1.5%, it indicates that the crystal nuclei have begun to solidify. This threshold serves as the basis for configuring the quantitative parameters.

[0050] After the equipment is connected to the network, the control unit performs periodic calibration of the circulating water circuit through the circulating distribution pump. The system operates at a standard linear velocity of 0.08 m / s and collects the initial potential response value of the heterogeneous transition metal composite particle layer. The measured potential response value during operation and When the deviation rate reaches 5%, the automatic maintenance program is triggered. The program adjusts the pressure pulse amplitude through the circulating distribution pump. and with flux recovery rate To optimize the objective, optimization is performed, among which, Flux after flushing Flux before flushing The ratio of the system's pressure pulse amplitudes is used to traverse the system's pressure pulse amplitudes. Found The optimal amplitude at that time, and compare this amplitude with the corresponding hardness. The associated data is written to non-volatile memory to form a dynamic calibration matrix. When subsequent monitoring of circulating water quality... When fluctuations occur, the system calls the optimal control parameters in the matrix to automatically correct the operating voltage and pressure pulse cycle of the electrochemical treatment unit, so that the electrochemical activity of the treatment unit is maintained within the effective operating range. The above calibration and adaptive adjustment procedures realize the self-repair of system performance for different regional water quality characteristics and ensure the hydraulic resistance stability of the filtration unit under long-term operation.

[0051] 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.

[0052] 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 multi-stage water treatment process for pet water purification, characterized in that, Includes the following steps: Step S1: Control the circulating fluid to be treated to pass through the tertiary amine functional group modified porous matrix bed at an initial linear velocity of 0.05 m / s to 0.12 m / s, and control the hydraulic residence time of the circulating fluid to be treated in the tertiary amine functional group modified porous matrix bed to be 1.5 s to 3.0 s. Step S2: The circulating fluid to be treated after being modified by the tertiary amine functional group into the heterogeneous transition metal composite particle layer is introduced into the heterogeneous transition metal composite particle layer. The heterogeneous transition metal composite particle layer is composed of active copper particles with a particle size of 0.5 mm to 1.2 mm and active zinc particles with a particle size of 0.5 mm to 1.2 mm in a mass ratio of 1:2.5 to 1:4.

0. Step S3: By adjusting the output power of the fluid circulation power unit, the linear velocity of the circulating fluid to be processed in the heterogeneous transition metal composite particle layer is increased stepwise from the initial linear velocity to 0.6 m / s to 1.5 m / s, and the duration of each stepwise increase is 3 s to 10 s. Step S4: The circulating fluid to be treated after passing through the heterogeneous transition metal composite particle layer is introduced into a porous carbon composite adsorption unit with an average micropore diameter of 1.5 nm to 4.5 nm and a specific surface area of ​​800 m² / g to 1300 m² / g, and the flow rate of the circulating fluid to be treated in the porous carbon composite adsorption unit is controlled to be 0.02 m / s to 0.08 m / s.

2. The multi-stage water treatment process for pet drinking water purification according to claim 1, characterized in that, Under the conditions of the initial linear velocity controlled in step S1 and the mass ratio configured in step S2, the density of tertiary amine functional groups on the surface of the tertiary amine functional group modified porous matrix bed is 0.45 mmol / g to 0.85 mmol / g, the packing density of the tertiary amine functional group modified porous matrix bed is 0.62 g / cm³ to 0.78 g / cm³, and the average pore size is 10 μm to 35 μm; in step S2, the purity of the active copper particles is not less than 99.9%, the purity of the active zinc particles is not less than 99.9%, and the surface roughness of the active copper particles and active zinc particles in the heterogeneous transition metal composite particle layer is... The range is from 0.8 μm to 2.5 μm.

3. The multi-stage water treatment process for purifying pet drinking water according to claim 1, characterized in that, Regarding the control of fluid linear velocity in step S3, step S3 includes the following refined sub-steps: Step S31, the conductivity fluctuation rate and layer resistance pressure drop parameters of the circulating fluid to be processed are collected through the fluid parameter acquisition unit; Step S32, when the conductivity fluctuation rate continuously exceeds 1.5% within 120s and the layer resistance pressure drop parameter exceeds the calibrated resistance threshold of 0.02MPa, it is determined that the surface of the heterogeneous transition metal composite particle layer has reached the upper limit of scaling resistance and a power adjustment trigger signal is issued; Step S33, in response to the power adjustment trigger signal, the driving frequency of the fluid circulation power unit is adjusted so that the output power of the fluid circulation power unit is increased from the reference power to the excitation power within 1.5s, and the fluid linear velocity is increased to the numerical range of the step acceleration rate.

4. The multi-stage water treatment process for pet drinking water purification according to claim 1, characterized in that, The tertiary amine functional group-modified porous matrix bed introduced in step S1 is prepared through the following refined sub-steps: Step S11, porous aluminosilicate ceramic particles are immersed in a 3% to 8% (w / w) 3-aminopropyltriethoxysilane ethanol solution and reacted at a constant temperature of 50°C to 65°C for 2 to 4 hours to complete silanization. After filtration and drying, a solid intermediate is obtained. Step S12, the solid intermediate is introduced into a mixed reaction system of formaldehyde and formic acid and reacted at a constant temperature of 80°C to 95°C for 4 to 8 hours to complete methylation, so that tertiary amine functional groups are grafted onto the surface of the porous aluminosilicate ceramic particles. After filtration, washing and drying, a tertiary amine functional group-modified porous matrix bed is obtained.

5. A multi-stage water treatment process for purifying pet drinking water according to claim 1, characterized in that, In step S4, when the porous carbon composite adsorption unit intercepts small molecule denatured products, the porous carbon composite adsorption unit is composed of activated coconut shell activated carbon and bone char mixed in a mass ratio of 2:1 to 5:

1. The total pore volume of the porous carbon composite adsorption unit is 0.65 cm³ / g to 0.92 cm³ / g, and the proportion of micropores with a pore size of less than 2 nm to the total pore volume is 75% to 88%.

6. A multi-stage water treatment process for purifying pet drinking water according to claim 1, characterized in that, In step S1, the protein concentration in the circulating fluid to be treated is between 15 mg / L and 85 mg / L. After step S1, the retention rate of macromolecular organic matter in the circulating fluid to be treated is not less than 92%.

7. A multi-stage water treatment process for purifying pet drinking water according to claim 1, characterized in that, In step S2, the particle size of the active copper particles is 0.6 mm to 1.0 mm, the particle size of the active zinc particles is 0.6 mm to 1.0 mm, and the filling height of the heterogeneous transition metal composite particle layer composed of the mixture of active copper particles and active zinc particles is 60 mm to 120 mm.

8. A multi-stage water treatment process for purifying pet drinking water according to claim 1, characterized in that, In step S3, under the shear condition where the fluid linear velocity increases by a step, the transient shear stress generated inside the heterogeneous transition metal composite particle layer is controlled to be between 1.2 Pa and 3.8 Pa. The contact interface between the active copper particles and the active zinc particles is cleaned by the transient shear stress to reduce the fluid flow resistance.

9. A multi-stage water treatment process for purifying pet drinking water according to claim 1, characterized in that, In step S4, the circulating fluid to be treated passes through the drainage branch path after the porous carbon composite adsorption unit, so that the hydraulic residence time of the circulating fluid to be treated in the porous carbon composite adsorption unit is stabilized within the range of 2.0s to 5.0s, and the circulating fluid to be treated is introduced into the light-proof and sealed material channel.

Images