An integrated device for co-production of active components of eggshell membrane and a preparation method thereof

Abstract

The application discloses an integrated device for co-production of active components of eggshell membrane and a preparation method thereof, and relates to the technical field of egg by-product processing. The integrated device comprises an intelligent control unit, a subcritical water-enzymatic decoupling unit, an online calcium ion removal unit and a multistage membrane separation unit. The subcritical water-enzymatic decoupling unit comprises a pressure-resistant reaction kettle, wherein an ultrasonic probe, a temperature sensor, a temperature gradient controller, a pH sensor and a pH real-time controller are integrated. The online calcium ion removal unit comprises a cation exchange resin column filled with carboxymethyl cellulose carriers. The multistage membrane separation unit comprises membrane assemblies connected in series. The intelligent control unit comprises a data acquisition module, an AI optimization module and a control execution module. The application realizes comprehensive utilization of eggshell membrane waste, significantly reduces pollution emissions in the production process, and has significant technical innovation, industrial practicality and economic benefits.

Description

Technical Field

[0001] This application relates to the field of egg by-product processing technology, and in particular to an intelligent integrated equipment and method for the co-production of active components in eggshell membranes. Background Technology

[0002] Eggshell membranes, a major waste product of the poultry egg processing industry, have a global annual output of over 8 million tons. Eggshell membranes contain a variety of high-value natural bioactive components, including approximately 10% collagen, 80% elastin, 1%-2% hyaluronic acid, chondroitin sulfate, and calcium ions. These active components have extremely high application value in fields such as biomedicine, skin care, and food health care, making them a natural biological resource with great development potential. Realizing their high-value comprehensive utilization has become a research hotspot in the field of resource utilization of poultry egg processing waste.

[0003] Currently, the industry's extraction technology for active components in eggshell membranes mainly relies on traditional processes such as acid hydrolysis, alkaline hydrolysis, or reducing agent pretreatment followed by enzymatic hydrolysis. While this approach can achieve preliminary extraction of collagen, it has significant technical drawbacks: Firstly, the acids, alkalis, and reducing agents used in the pretreatment process can easily leave chemical reagent residues in the product, which can not only cause cytotoxicity issues in subsequent applications but also damage the molecular structure of active polysaccharides such as hyaluronic acid and chondroitin sulfate, leading to their loss of biological activity. Secondly, these processes primarily focus on extracting collagen alone, failing to achieve the simultaneous recovery and graded co-production of multiple high-value active components such as hyaluronic acid, chondroitin sulfate, and shell membrane peptides from eggshell membranes, resulting in secondary waste of resources.

[0004] Membrane separation technology, due to its high efficiency, mildness, and ease of continuous operation, has been attempted for application in the fractional purification of active components from eggshell membranes, hoping to solve the problem of product homogeneity caused by traditional processes. However, the application of membrane separation technology still faces bottlenecks: the high calcium ion content naturally present in eggshell membranes easily forms complexes with active components, and the resulting complex precipitates cause severe fouling of the membrane module, leading to a rapid decline in membrane flux. To maintain separation efficiency, frequent chemical cleaning of the membrane module is required, which not only significantly increases equipment maintenance and consumable replacement costs but also introduces new pollutants due to the use of chemical cleaning reagents. At the same time, the existing eggshell membrane extraction process is highly open, generating a large amount of highly polluting wastewater and solid waste during extraction, separation, and cleaning. The wastewater COD (chemical oxygen demand) value is ≥8000 mg / L, accompanied by a large amount of acid sludge. The subsequent treatment costs for wastewater and solid waste are high, which contradicts the current green and low-carbon industrial development concept.

[0005] It is evident that existing technologies for extracting active components from eggshell membranes still face numerous technical challenges that urgently need to be addressed. The problem of efficient, continuous, and synergistic extraction of active components under calcium interference has not yet been effectively overcome. Furthermore, there is currently no dedicated integrated and intelligent equipment in the industry capable of achieving fully enclosed, continuous co-production of multiple components such as shell membrane collagen peptides, hyaluronic acid, and chondroitin sulfate, as well as efficient online removal of calcium ions. This results in low levels of comprehensive utilization of eggshell membrane resources and poor industrial economic benefits, hindering the large-scale and green development of the eggshell membrane waste resource utilization industry. Summary of the Invention

[0006] This application provides an intelligent integrated equipment and method for the co-production of active components from eggshell membranes, in order to solve the problems in the prior art.

[0007] On one hand, embodiments of this application provide an integrated intelligent equipment for the co-production of active components from eggshell membranes, comprising: The system includes an intelligent control unit and an execution unit. The execution unit comprises a subcritical water-enzyme hydrolysis coupling unit, an online calcium ion removal unit, and a multi-stage membrane separation unit. The execution unit is internally connected via pipes and pumps. The intelligent control unit is signal-connected to the execution unit. The subcritical water-enzyme hydrolysis coupling unit includes a pressure-resistant reactor, which integrates an ultrasonic probe, a temperature sensor, a temperature gradient controller, a pH sensor, and a real-time pH regulator; a storage tank for temporarily storing the extract is provided between the subcritical water-enzyme hydrolysis coupling unit and the online calcium ion removal unit. The online calcium ion removal unit includes a cation exchange resin column filled with carboxymethyl cellulose support, which is used to adsorb calcium ions in the extract. The multi-stage membrane separation unit includes membrane modules connected in series, which are used to retain and extract retentate containing active components; The intelligent control unit includes a data acquisition module, an AI optimization module, and a control execution module. The data acquisition module is used to collect real-time reaction data inside the pressure-resistant reactor. The AI ​​optimization module has a built-in trained machine learning model, which is used to dynamically predict and optimize process parameters based on real-time reaction data. The control execution module is used to send the optimized process parameters to the execution unit for adaptive control.

[0008] Furthermore, the working pressure of the pressure-resistant reactor is 1.0-3.0 MPa, the working frequency of the ultrasonic probe is 40 kHz, the temperature gradient controller controls the reaction temperature in the range of 110-180℃, and the real-time pH controller controls the pH value in the range of 6.5-7.5.

[0009] Furthermore, the membrane module includes: a ceramic microfiltration membrane with a pore size of 0.45 μm, a first polyethersulfone ultrafiltration membrane with a molecular weight cutoff of 100 kDa, a second polyethersulfone ultrafiltration membrane with a molecular weight cutoff of 30 kDa, and a nanofiltration membrane with a molecular weight cutoff of 200 Da.

[0010] Furthermore, the intelligent control unit also includes a membrane fouling prediction module, which is used to predict membrane fouling trends based on historical data of transmembrane pressure difference and membrane flux, and trigger cleaning alarms and automatic cleaning programs.

[0011] Furthermore, the multi-stage membrane separation unit also includes a temperature protection system integrated outside the membrane housing of the membrane module. The temperature protection system is used to activate rapid cooling when the temperature of the feed liquid entering the membrane module exceeds a set threshold.

[0012] On the other hand, embodiments of this application also provide an intelligent method for the co-production of active components from eggshell membranes, comprising: Eggshell membrane fragments from egg processing waste are processed to obtain eggshell membrane fragments that meet the preparation standards. The feed solution containing the processed eggshell membrane fragments and deionized water is added to the subcritical water-enzyme hydrolysis coupling unit. Based on the raw material characteristics of eggshell membrane fragments in the feed liquid, the intelligent control unit calls the AI ​​optimization module to set the subcritical water pretreatment parameters, and the subcritical water-enzymatic hydrolysis coupling unit executes the subcritical water pretreatment parameters in the pressure-resistant reactor. After pretreatment, the liquid is cooled to the set temperature by a temperature gradient controller. The compound protease is added to the liquid that meets the set temperature requirements, and the enzymatic hydrolysis reaction is carried out under ultrasonic stirring conditions using an ultrasonic probe to obtain the hydrolysate. The enzymatic hydrolysate is processed by an online calcium ion removal unit to remove calcium ions, resulting in a decalcified solution. The decalcification solution is separated step by step through a multi-stage membrane separation unit to obtain a retentate containing hyaluronic acid, a retentate containing shell membrane peptides, and a retentate containing chondroitin sulfate. The retentate containing hyaluronic acid, the retentate containing shell membrane peptides, and the retentate containing chondroitin sulfate were post-processed to obtain hyaluronic acid products, shell membrane peptide products, and chondroitin sulfate products, respectively.

[0013] Further, the raw material processing involves washing and drying eggshell membrane fragments until the moisture content is <10%, then crushing them to a particle size of 1-2 mm; the weight ratio of the processed eggshell membrane fragments to deionized water is 1:10 to 1:25; the subcritical water pretreatment parameters are: temperature 120-150℃, pressure 1.0-2.5MPa, time 20-60 minutes; a temperature gradient controller cools the solution to 35-50℃; the enzymatic hydrolysis reaction time is 2-10 hours; and calcium ion removal is performed to achieve a calcium ion removal rate ≥90%.

[0014] Further, the stepwise separation includes: the decalcification solution is initially filtered through a ceramic microfiltration membrane to obtain a microfiltration clarified solution; the microfiltration clarified solution is retained through a first polyethersulfone ultrafiltration membrane to obtain a retentate containing hyaluronic acid and a first permeate; the first permeate is retained through a second polyethersulfone ultrafiltration membrane to obtain a retentate containing shell membrane peptides and a second permeate; the second permeate is retained through a nanofiltration membrane to obtain a retentate containing chondroitin sulfate and a final permeate; the final permeate is recyclable small molecule peptides and amino acids.

[0015] Further, the post-processing includes: adding ethanol to the retentate containing hyaluronic acid to precipitate hyaluronic acid, centrifuging and drying to obtain hyaluronic acid product; freeze-drying the retentate containing shell membrane peptides to obtain shell membrane peptide product; and spray-drying or freeze-drying the retentate containing chondroitin sulfate to obtain chondroitin sulfate product.

[0016] Furthermore, the intelligent control unit calls the AI ​​optimization module to set the subcritical water pretreatment parameters, including: the AI ​​optimization module calls the built-in machine learning model to optimize the subcritical water temperature, pretreatment time, and enzymatic hydrolysis time according to the characteristics of the currently input raw materials, and automatically issues the execution.

[0017] The intelligent integrated equipment and method for the co-production and preparation of active components from eggshell membranes disclosed in this application have the following advantages: This technology overcomes the limitations of existing methods involving separate enzymatic hydrolysis and subcritical water extraction. By integrating equipment to create a synergistic effect, the yield of active components is significantly improved compared to individual processing methods, fundamentally solving the problem of low extraction efficiency in existing technologies. A dedicated online calcium ion removal unit effectively avoids the formation of precipitates by high calcium ion content in eggshell membranes, preventing membrane contamination and eliminating the adverse effects of calcium ions on product purity. This addresses the core bottleneck of applying existing membrane separation technology to eggshell membrane extraction. Multi-membrane separation enables the simultaneous separation and co-production of high-value active components, with the final permeate being recyclable. This solves the problems of single product and secondary resource waste in existing technologies, achieving diversified and high-value utilization of eggshell membrane resources. Utilizing an intelligent control unit centered on an industrial computer for full-process monitoring, compared to the manual control mode of existing technologies, this achieves intelligent and adaptive control of the entire process, significantly improving process stability and production efficiency while reducing manual maintenance costs.

[0018] It is evident that the integrated equipment and preparation method proposed in this application, through the technical means of eliminating calcium interference, efficiently extracting active components, precisely co-producing multiple components, and intelligently controlling the entire process, not only significantly improves the extraction rate of active components from eggshell membranes and realizes the high-value comprehensive utilization of eggshell membrane waste, but also significantly reduces pollution emissions during the production process. It provides dedicated equipment and process support for the large-scale and green development of the eggshell membrane resource utilization industry, and possesses significant technological innovation, industrial applicability, and economic benefits. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 A schematic diagram of the structure of the integrated device provided in the embodiments of this application.

[0021] Explanation of reference numerals: 1. Feed inlet; 2. pH sensor; 3. Ultrasonic probe; 4. Temperature sensor; 5. Media inlet; 6. Ceramic filter plate; 7. Solid residue outlet; 8. Media outlet; 9. Discharge outlet; 10. Centrifugal pump; 11. Storage tank; 12. Feed inlet; 13. Cation exchange resin column; 14. Feed outlet; 15. Semiconductor refrigeration chip; 16. Ceramic microfiltration membrane; 17. Filter residue outlet; 18. First polyethersulfone ultrafiltration membrane; 19. First retentate outlet; 20. Second polyethersulfone ultrafiltration membrane; 21. Second retentate outlet; 22. Nanofiltration membrane; 23. Third retentate outlet; 24. Filtrate outlet; 25. Pressure sensor; 26. Automated control equipment. Detailed Implementation

[0022] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0023] Figure 1 This is a schematic diagram of the integrated device structure provided in an embodiment of this application. This application provides an intelligent integrated device for the co-production of active components from eggshell membranes, comprising: an intelligent control unit and an execution unit. The execution unit includes a subcritical water-enzyme decoupling unit, an online calcium ion removal unit, and a multi-stage membrane separation unit. The execution unit is internally connected via pipes and pumps. The intelligent control unit is signal-connected to the execution unit. The subcritical water-enzyme hydrolysis coupling unit includes a pressure-resistant reactor, which integrates an ultrasonic probe 3, a temperature sensor 4, a temperature gradient controller, a pH sensor 2, and a real-time pH regulator; a storage tank 11 for temporarily storing the extract is provided between the subcritical water-enzyme hydrolysis coupling unit and the online calcium ion removal unit. The online calcium ion removal unit includes a cation exchange resin column 13 filled with a carboxymethyl cellulose support, which is used to adsorb calcium ions in the extract. The multi-stage membrane separation unit includes membrane modules connected in series, which are used to retain and extract retentate containing active components; The intelligent control unit includes a data acquisition module, an AI optimization module, and a control execution module. The data acquisition module is used to collect real-time reaction data inside the pressure-resistant reactor. The AI ​​optimization module has a built-in trained machine learning model, which is used to dynamically predict and optimize process parameters based on real-time reaction data. The control execution module is used to send the optimized process parameters to the execution unit for adaptive control.

[0024] For example, the integrated device proposed in this application mainly consists of the following four units: Subcritical Water-Enzymatic Hydrolysis Coupling Unit: This unit is the core for achieving efficient extraction. It includes a pressure-resistant reactor, which integrates an ultrasonic probe 3, a temperature sensor 4 with a temperature gradient controller, and a pH sensor 2 with a real-time pH regulator. The ultrasonic probe 3 generates cavitation during the subcritical water pretreatment stage, violently impacting the eggshell membrane fiber structure and promoting mass transfer and component release during the enzymatic hydrolysis reaction. The temperature sensor 4 and temperature gradient controller precisely control the reaction temperature within the set range and enable rapid heating and cooling. Temperature control is achieved through a heat transfer medium, which circulates heat through the medium inlet 5 and medium outlet 8. The pH sensor 2 and real-time pH regulator automatically add dilute acid or alkali solutions to stabilize the pH of the extraction system within the optimal range, inhibiting excessive collagen denaturation under subcritical water conditions and providing a suitable environment for subsequent enzymatic hydrolysis.

[0025] The subcritical water-enzymatic hydrolysis coupling unit is also equipped with an inlet 1, an outlet 9, and a dedicated enzyme preparation addition port. Inlet 1 is connected to the feed system, and outlet 9 is connected to the storage tank 11 via a pipe and pump. After enzymatic hydrolysis, the extract is processed through a ceramic filter plate 6 and discharged through the solid residue outlet 7. Incompletely hydrolyzed eggshell membrane residue is retained in the reactor to prevent large particles from entering the subsequent decalcification column and membrane module, thus preventing physical blockage.

[0026] Online calcium ion removal unit: This unit is connected to storage tank 11 via pipes and a pump. Centrifugal pump 10 in the pipes pressurizes and delivers the extract flowing through the pipes. Considering that enzymatic hydrolysis is a batch operation and membrane separation is a continuous operation, storage tank 11 is provided for temporary storage of the extract, decoupling the upstream batch reaction from the downstream continuous separation, thereby achieving flow matching.

[0027] The online calcium ion removal unit includes a cation exchange resin column 13 filled with carboxymethyl cellulose support. The feed solution enters the unit through the feed inlet 12. When passing through the cation exchange resin column 13, calcium ions are efficiently adsorbed and removed, effectively avoiding the adverse effects of calcium ions on subsequent membrane separation processes and product purity. The decalcified solution is output to the multi-stage membrane separation unit through the feed outlet 14.

[0028] Multi-stage membrane separation unit: This unit consists of membrane modules connected in series to achieve continuous separation. The membrane modules include a ceramic microfiltration membrane 16, a first polyethersulfone ultrafiltration membrane 18, a second polyethersulfone ultrafiltration membrane 20, and a nanofiltration membrane 22. The ceramic microfiltration membrane 16 removes residual insoluble particles, bacteria, and other impurities; these impurities are discharged through the filter residue outlet 17. The first polyethersulfone ultrafiltration membrane 18 retains high-molecular-weight hyaluronic acid; the resulting retentate containing hyaluronic acid is discharged through the first retentate outlet 19. The second polyethersulfone ultrafiltration membrane 20 retains medium-molecular-weight shell peptides; the resulting retentate containing shell peptides is discharged through the second retentate outlet 21. The nanofiltration membrane 22 concentrates small-molecule chondroitin sulfate and oligopeptides, while removing some salts and water; the retentate containing chondroitin sulfate is discharged through the third retentate outlet 23. After treatment by the nanofiltration membrane 22, the final permeate is discharged through the filtrate outlet 24.

[0029] Considering that the rate of increase of transmembrane pressure difference is a core characterization parameter of membrane fouling, a pressure sensor 25 is installed above each membrane module to monitor the inlet pressure of each membrane module. This pressure value, combined with membrane flux data, can be used to calculate the transmembrane pressure difference.

[0030] The temperature protection system is integrated outside the membrane housing of each membrane module in the multi-stage membrane separation unit. It employs a high-performance semiconductor cooling chip 15 (such as a thermoelectric cooler based on the Peltier effect). This system activates rapid cooling when the temperature of the feed solution entering the membrane module exceeds a set threshold. Specifically, when a high-temperature feed solution exceeding the set threshold flows in from the previous unit, the system can rapidly reduce the temperature of the feed solution from as high as 180°C to 40°C within 5 minutes, ensuring production efficiency and the bioactivity of the product.

[0031] Intelligent control unit: includes data acquisition module, AI optimization module and control execution module.

[0032] The intelligent control unit, centered on an industrial computer, connects to all sensors and actuators via a data interface. On the central control platform, users can set preparation goals, such as maximizing hyaluronic acid yield. After system startup, the AI ​​optimization module invokes a built-in machine learning model—specifically, a digital twin model—to calculate the optimal subcritical water temperature, processing time, and best enzymatic hydrolysis time based on the characteristics of the currently input eggshell membrane raw material, and automatically sends these process parameters for execution. Throughout the production process, an online spectrometer monitors the hydrolysate composition in real time. If the shell membrane peptide concentration growth curve reaches a plateau prematurely, the AI ​​optimization module makes dynamic decisions, choosing to terminate the enzymatic hydrolysis early and proceed to the next stage, thereby saving energy and time.

[0033] Meanwhile, the intelligent control unit also includes a membrane fouling prediction module. This module predicts membrane fouling trends based on historical data of transmembrane pressure difference and membrane flux, triggering cleaning alarms and automatic cleaning procedures. By analyzing the flux decay rate of the ultrafiltration membrane in real time, the membrane fouling prediction module sends an early warning to maintenance personnel and automatically prepares for cleaning when the predicted remaining service life is less than 10%.

[0034] The integrated equipment proposed in this application is made entirely of stainless steel, which is corrosion-resistant and easy to clean. Each unit is monitored for parameters and controlled by an automated control device 26 (such as a programmable logic controller, PLC).

[0035] In one possible implementation, the pressure vessel operates at a pressure of 1.0-3.0 MPa, the ultrasonic probe 3 operates at a frequency of 40 kHz, the temperature gradient controller controls the reaction temperature within the range of 110-180℃, and the real-time pH controller controls the pH value within the range of 6.5-7.5.

[0036] In one possible implementation, the ceramic microfiltration membrane 16 has a pore size of 0.45 μm, the first polyethersulfone ultrafiltration membrane 18 has a molecular weight cutoff of 100 kDa, the second polyethersulfone ultrafiltration membrane 20 has a molecular weight cutoff of 30 kDa, and the nanofiltration membrane 22 has a molecular weight cutoff of 200 Da.

[0037] This application also provides an intelligent method for the co-production of active components from eggshell membranes, including: Eggshell membrane fragments from egg processing waste are processed to obtain eggshell membrane fragments that meet the preparation standards. The feed solution containing the processed eggshell membrane fragments and deionized water is added to the subcritical water-enzyme hydrolysis coupling unit. Based on the raw material characteristics of eggshell membrane fragments in the feed liquid, the intelligent control unit calls the AI ​​optimization module to set the subcritical water pretreatment parameters, and the subcritical water-enzymatic hydrolysis coupling unit executes the subcritical water pretreatment parameters in the pressure-resistant reactor. After pretreatment, the liquid is cooled to the set temperature by a temperature gradient controller. The compound protease is added to the liquid that meets the set temperature requirements, and the enzymatic hydrolysis reaction is carried out under ultrasonic stirring conditions using ultrasonic probe 3 to obtain the hydrolysate. The enzymatic hydrolysate is processed by an online calcium ion removal unit to remove calcium ions, resulting in a decalcified solution. The decalcification solution is separated step by step through a multi-stage membrane separation unit to obtain a retentate containing hyaluronic acid, a retentate containing shell membrane peptides, and a retentate containing chondroitin sulfate. The retentate containing hyaluronic acid, the retentate containing shell membrane peptides, and the retentate containing chondroitin sulfate were post-processed to obtain hyaluronic acid products, shell membrane peptide products, and chondroitin sulfate products, respectively.

[0038] Specifically, the raw material processing of eggshell membrane fragments involves washing and drying the fragments until the moisture content is <10%, then crushing them to a particle size of 1-2 mm. The weight ratio of the processed eggshell membrane fragments to deionized water is 1:10 to 1:25. The subcritical water pretreatment parameters are: temperature 120-150℃, pressure 1.0-2.5MPa, and time 20-60 minutes. A temperature gradient controller is used to cool the solution to 35-50℃. The enzymatic hydrolysis reaction takes 2-10 hours. Calcium ions are removed to achieve a removal rate ≥90%.

[0039] The above-mentioned stepwise separation includes: the decalcification solution is initially filtered through a ceramic microfiltration membrane 16 to obtain a microfiltration clarified solution; the microfiltration clarified solution is retained through a first polyethersulfone ultrafiltration membrane 18 to obtain a retentate containing hyaluronic acid and a first permeate; the first permeate is retained through a second polyethersulfone ultrafiltration membrane 20 to obtain a retentate containing shell membrane peptides and a second permeate; the second permeate is retained through a nanofiltration membrane 22 to obtain a retentate containing chondroitin sulfate and a final permeate; the final permeate is recyclable small molecule peptides and amino acids.

[0040] The above post-processing includes: adding ethanol to the retentate containing hyaluronic acid to precipitate hyaluronic acid, centrifuging and drying to obtain hyaluronic acid product; freeze-drying the retentate containing shell membrane peptides to obtain shell membrane peptide product; and spray-drying or freeze-drying the retentate containing chondroitin sulfate to obtain chondroitin sulfate product.

[0041] Furthermore, the intelligent control unit calls the AI ​​optimization module to set subcritical water pretreatment parameters, including: the AI ​​optimization module calls the built-in machine learning model to optimize process parameters such as subcritical water temperature, pretreatment time, and enzymatic hydrolysis time based on the characteristics of the currently input raw materials, and automatically issues the commands for execution.

[0042] In Example 1, the steps for the co-production of eggshell membrane active components using the method proposed in this application are as follows: (1) Raw material processing: Take the eggshell membrane, a by-product of the egg liquid processing plant, and after thorough cleaning, dry it in a 50℃ oven to constant weight. Then, use a pulverizer to crush it into powder with a particle size of 1mm for later use.

[0043] (2) Subcritical water pretreatment: Weigh 100g of the above-mentioned eggshell membrane powder, add deionized water at a material-to-liquid weight ratio of 1:15, and put it into the subcritical water-enzyme hydrolysis coupling unit. Close the pressure-resistant reactor, and set the subcritical water pretreatment conditions as follows according to the instructions of the intelligent control unit: temperature 140℃, pressure 1.2MPa, time 20 minutes. Start the ultrasonic probe (40kHz) and pH regulator (maintain pH 7.0). In this stage, the synergistic effect of the high temperature and high pressure of the subcritical water and the ultrasound can effectively break the hydrogen bonds and some covalent bonds in the eggshell membrane, making it loose and exposing more enzyme action sites.

[0044] (3) Rapid cooling and enzymatic hydrolysis: After pretreatment, the rapid cooling system and temperature protection system of the reactor were immediately activated to reduce the material temperature to 40°C within 5 minutes. Subsequently, 0.5% (w / w) of a complex protease of trypsin and papain was added through the enzyme addition port. Enzymatic hydrolysis was carried out for 4 hours at a temperature of 40°C with continuous ultrasonic (40kHz) stirring. Ultrasonic stirring not only maintains the uniformity of the system but also continuously physically breaks down the material, accelerating the enzymatic hydrolysis process.

[0045] (4) Online decalcification: After enzymatic hydrolysis, the extract was pumped to the online calcium ion removal unit at a flow rate of 15 mL / min. After passing through the carboxymethyl cellulose cation exchange resin column, calcium ions were adsorbed. The calcium ion removal rate in the extract was 93% as detected by ICP-MS (inductively coupled plasma mass spectrometry).

[0046] (5) Multistage membrane separation and product preparation: The decalcified solution first passes through a ceramic microfiltration membrane 16 with a pore size of 0.45 μm to obtain a microfiltration clarified solution. The microfiltration clarified solution enters a first polyethersulfone ultrafiltration membrane 18 with a molecular weight cutoff of 100 kDa, and the retentate is mainly high molecular weight hyaluronic acid. Three volumes of 95% ethanol are added to the retentate, and after precipitation, centrifugation, and vacuum drying, 0.75 g of hyaluronic acid product is obtained. The first permeate obtained by filtration enters a second polyethersulfone ultrafiltration membrane 20 with a molecular weight of 30 kDa, and the retentate is mainly shell membrane peptides. The retentate is freeze-dried to obtain 3.2 g of shell membrane peptide product. The second permeate obtained by filtration enters a nanofiltration membrane 22 with a molecular weight of 200 Da, and the retentate is spray-dried to obtain 0.35 g of chondroitin sulfate product.

[0047] In Example 2, the steps for the co-production of eggshell membrane active components using the method proposed in this application are as follows: The subcritical water pretreatment conditions were set as follows: temperature 145℃, pressure 1.8 MPa, time 50 minutes, pH 7.2, and the remaining steps and parameters were exactly the same as in the previous embodiment.

[0048] The results showed that the yield of hyaluronic acid increased to 0.85g hyaluronic acid / 100g raw material, the yield of shell membrane peptides increased to 3.8g shell membrane peptides / 100g raw material, and the yield of chondroitin sulfate increased to 0.42g chondroitin sulfate / 100g raw material.

[0049] In Comparative Example 1, the steps for preparing the active components of the eggshell membrane using a single enzymatic hydrolysis process are as follows: Except for the absence of subcritical water pretreatment, the remaining steps are exactly the same as those in Example 2. That is, the eggshell membrane powder is directly mixed with water, the pH and temperature are adjusted, and then enzymatic hydrolysis is carried out for 4 hours.

[0050] Results: The final yields were 0.25 g hyaluronic acid, 1.5 g shell membrane peptides, and 0.08 g chondroitin sulfate. The yields of each component were significantly lower than those in Examples 1 and 2.

[0051] In Comparative Example 2, the steps for preparing the active components of the eggshell membrane using a separate subcritical water process are as follows: Except for the omission of the enzymatic hydrolysis process, the remaining steps are exactly the same as those in Example 2. That is, after subcritical water pretreatment, decalcification and membrane separation are performed directly.

[0052] Results: The final yield was 0.60 g of hyaluronic acid, 1.8 g of shell membrane peptides, and 0.20 g of chondroitin sulfate. Although the overall yield was higher than that of enzymatic hydrolysis alone, it was still lower than that of the coupled process.

[0053] The results of Example 2 and the two comparative examples are summarized in Table 1.

[0054] Table 1 Comparison of results between Example 2 and the comparative example.

[0055] The comparative data clearly show that the subcritical water-enzyme hydrolysis coupling process proposed in this application is significantly superior to either enzymatic hydrolysis alone or subcritical water alone in terms of the yield of hyaluronic acid, shell membrane peptides, and chondroitin sulfate. This fully demonstrates the synergistic effect of the coupling unit, the core innovation of this application: that is, the subcritical water pretreatment plays a key role in cell wall disruption and activation, destroying the physical barrier of the eggshell membrane and creating extremely favorable conditions for subsequent enzymatic hydrolysis; the enzymatic hydrolysis process, under mild conditions, specifically and efficiently cuts the activated substrate, thereby achieving high-yield extraction of the target active components.

[0056] Therefore, the integrated equipment and method proposed in this application not only realize the high-value comprehensive utilization of eggshell membrane resources, but also solve the problems of low extraction efficiency, single product, and calcium ion interference in the grading of existing technologies through process coupling.

[0057] Although preferred embodiments of this application have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of this application.

[0058] Obviously, those skilled in the art can make various modifications and variations to this application without departing from the spirit and scope of this application. Therefore, if such modifications and variations fall within the scope of the claims of this application and their equivalents, this application also intends to include such modifications and variations.

Claims

1. An intelligent integrated equipment for the co-production and preparation of active components from eggshell membranes, characterized in that, include: The system includes an intelligent control unit and an execution unit. The execution unit comprises a subcritical water-enzyme hydrolysis coupling unit, an online calcium ion removal unit, and a multi-stage membrane separation unit. The execution unit is internally connected via pipes and a pump. The intelligent control unit is signal-connected to the execution unit. The subcritical water-enzyme hydrolysis coupling unit includes a pressure-resistant reactor, which integrates an ultrasonic probe (3), a temperature sensor (4), a temperature gradient controller, a pH sensor (2), and a real-time pH regulator. A storage tank (11) for temporarily storing the extract is provided between the subcritical water-enzyme hydrolysis coupling unit and the online calcium ion removal unit. The online calcium ion removal unit includes a cation exchange resin column (13) filled with a carboxymethyl cellulose carrier, the cation exchange resin column (13) being used to adsorb calcium ions in the extract. The multi-stage membrane separation unit includes membrane modules connected in series, the membrane modules being used to retain and extract retentate containing active components; The intelligent control unit includes a data acquisition module, an AI optimization module, and a control execution module. The data acquisition module is used to collect real-time reaction data inside the pressure-resistant reactor. The AI ​​optimization module has a built-in trained machine learning model, which is used to dynamically predict and optimize process parameters based on the real-time reaction data. The control execution module is used to send the optimized process parameters to the execution unit for adaptive control.

2. The intelligent integrated equipment for the co-production and preparation of active components from eggshell membranes according to claim 1, characterized in that, The working pressure of the pressure-resistant reactor is 1.0-3.0 MPa; the working frequency of the ultrasonic probe (3) is 40 kHz; the temperature gradient controller controls the reaction temperature at 110-180℃; and the real-time pH controller controls the pH value at 6.5-7.

5.

3. The intelligent integrated equipment for the co-production and preparation of active components from eggshell membranes according to claim 1, characterized in that, The membrane assembly includes: a ceramic microfiltration membrane (16) with a pore size of 0.45 μm, a first polyethersulfone ultrafiltration membrane (18) with a molecular weight cutoff of 100 kDa, a second polyethersulfone ultrafiltration membrane (20) with a molecular weight cutoff of 30 kDa, and a nanofiltration membrane (22) with a molecular weight cutoff of 200 Da.

4. The intelligent integrated equipment for the co-production and preparation of active components from eggshell membranes according to claim 1, characterized in that, The intelligent control unit also includes a membrane fouling prediction module, which is used to predict membrane fouling trends based on historical data of transmembrane pressure difference and membrane flux, and trigger cleaning alarms and automatic cleaning programs.

5. The intelligent integrated equipment for the co-production and preparation of active components from eggshell membranes according to claim 1, characterized in that, The multi-stage membrane separation unit also includes a temperature protection system integrated outside the membrane housing of the membrane module. The temperature protection system is used to activate rapid cooling when the temperature of the feed liquid entering the membrane module exceeds a set threshold.

6. A method for the co-production of active components from eggshell membranes using intelligent technology, characterized in that, The method is applied to the integrated device as described in any one of claims 1-5, and the method includes: Eggshell membrane fragments from egg processing waste are processed to obtain eggshell membrane fragments that meet the preparation standards. The feed solution containing the processed eggshell membrane fragments and deionized water is added to the subcritical water-enzyme hydrolysis coupling unit. Based on the raw material characteristics of the eggshell membrane fragments in the feed liquid, the intelligent control unit calls the AI ​​optimization module to set the subcritical water pretreatment parameters, and the subcritical water-enzyme hydrolysis coupling unit executes the subcritical water pretreatment parameters in the pressure-resistant reactor. After pretreatment, the liquid is cooled to the set temperature by a temperature gradient controller, and a complex protease is added to the liquid that meets the set temperature requirements. The enzymatic hydrolysis reaction is carried out under ultrasonic stirring conditions using an ultrasonic probe (3) to obtain the hydrolysate. The enzymatic hydrolysate is processed by the online calcium ion removal unit to remove calcium ions, resulting in a decalcified solution. The decalcification solution is separated step by step through a multi-stage membrane separation unit to obtain a retentate containing hyaluronic acid, a retentate containing shell membrane peptides, and a retentate containing chondroitin sulfate. The retentate containing hyaluronic acid, the retentate containing shell membrane peptides, and the retentate containing chondroitin sulfate were post-processed to obtain hyaluronic acid products, shell membrane peptide products, and chondroitin sulfate products, respectively.

7. The intelligent method for co-producing active components of eggshell membrane according to claim 6, characterized in that: The raw material processing involves washing and drying the eggshell membrane fragments until the moisture content is <10%, then crushing them to a particle size of 1-2 mm. The weight ratio of the processed eggshell membrane fragments to the deionized water is 1:10 to 1:

25. The subcritical water pretreatment parameters are: temperature 120-150℃, pressure 1.0-2.5MPa, and time 20-60 minutes. The temperature gradient controller cools the solution to 35-50℃. The enzymatic hydrolysis reaction lasts for 2-10 hours. The calcium ion removal process achieves a calcium ion removal rate of ≥90%.

8. The intelligent method for co-producing active components of eggshell membrane according to claim 6, characterized in that, The stepwise separation includes: the decalcification solution is initially filtered through a ceramic microfiltration membrane (16) to obtain a microfiltration clarified solution; the microfiltration clarified solution is retained through a first polyethersulfone ultrafiltration membrane (18) to obtain a retentate containing hyaluronic acid and a first permeate; the first permeate is retained through a second polyethersulfone ultrafiltration membrane (20) to obtain a retentate containing shell membrane peptides and a second permeate; the second permeate is retained through a nanofiltration membrane (22) to obtain a retentate containing chondroitin sulfate and a final permeate; the final permeate is a recyclable small molecule peptide and amino acid.

9. The intelligent method for co-producing active components of eggshell membrane according to claim 6, characterized in that, The post-processing includes: adding ethanol to the retentate containing hyaluronic acid to precipitate hyaluronic acid, centrifuging and drying to obtain a hyaluronic acid product; freeze-drying the retentate containing shell membrane peptides to obtain a shell membrane peptide product; and spray-drying or freeze-drying the retentate containing chondroitin sulfate to obtain a chondroitin sulfate product.

10. The intelligent method for co-producing active components of eggshell membrane according to claim 6, characterized in that, The intelligent control unit calls the AI ​​optimization module to set subcritical water pretreatment parameters, including: the AI ​​optimization module calls the built-in machine learning model to optimize the subcritical water temperature, pretreatment time, and enzymatic hydrolysis time according to the characteristics of the currently input raw materials, and automatically issues the execution.

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