Methods and equipment for shortening preparation cycle and synergistic regulation of interfacial tension in pectin electrochemical modification and emulsification enhancement

Abstract

This invention discloses a method and equipment for electrochemical modification and emulsification enhancement of pectin by shortening the preparation cycle and synergistically regulating interfacial tension. Experimental verification shows that this method can complete the structural modification of pectin within 60 minutes, significantly reducing the equilibrium interfacial tension of the modified pectin from 19.70 mN / m to 9.19 mN / m, and decreasing the average particle size of the tea oil emulsion from 2.14 μm to 1.16 μm. The supporting device utilizes a fixing frame with symmetrical cuboid grooves and metal pull rings to allow for flexible electrode insertion and removal and expansion of the electrode quantity. The electrochemical cell adopts a "bottom-in, top-out" double-layer sealed water bath structure, combined with magnetic stirring to ensure uniform field distribution and effectively avoid polysaccharide degradation caused by localized overheating. This invention combines the advantages of high efficiency, greenness, and precision, providing an advanced green technology solution for the precise modification and industrial application of polysaccharide biomacromolecules.

Description

Technical Field

[0001] This invention relates to the field of natural product modification technology, and in particular to a method and equipment for electrochemical modification and emulsification enhancement of pectin that shortens the preparation cycle and synergistically regulates interfacial tension. Background Technology

[0002] Pectin is a type of acidic heteropolysaccharide distributed in the primary cell walls and intercellular matrix of higher plants, accounting for 2-35% of the cell wall content, and is usually produced in the initial stage of cell wall growth. It acts as a hydrating agent and binder for cellulose network structures, making up about one-third of the dry matter of cell walls in dicotyledonous plants and some monocotyledonous plants. Pectin generally appears as a pale yellow or white powder and is one of the most important hydrophilic colloids in industrial production. Typically, pectin is mainly composed of four well-defined structural regions: homogalacturonic acid polysaccharide (HG), rhamnose-galacturonic acid polysaccharide type I (RG-I), rhamnose-galacturonic acid polysaccharide type II (RG-II), and xylose-galacturonic acid polysaccharide (XG).

[0003] HG is considered the "smooth" region of pectin, composed of D-galacturonic acid residues linked by α-(1,4)-glycosidic bonds, with both methoxy and acetylation occurring on the HG sequence. RG-I is known as the "hairy" region of pectin, consisting of alternating L-Rha and D-GalA residues. The side chains of the RG-I backbone vary depending on the pectin source. On the other hand, RG-II has a complex structure, consisting of up to 13 different monosaccharides linked by 21 glycosidic bonds. Based on the degree of methoxylation (DM), pectin can be divided into two categories: high-methoxyl pectin (HMP, DM>50%) and low-methoxyl pectin (LMP, DM<50%). HMP can form gels at low pH and high sucrose concentrations, while LMP can form gels in the presence of polyvalent cations using an "egg carton" model.

[0004] To date, pectin has been widely used in the food and pharmaceutical industries due to its long-standing safety record, biocompatibility, and biodegradability. Typically, pectin serves as a natural additive, possessing emulsifying, stabilizing, and thickening properties to improve the quality and texture of food. Furthermore, epidemiological studies have shown that pectin can alleviate colonic inflammation and also relieve metabolic disorders such as type 2 diabetes, obesity, and non-alcoholic fatty liver disease. In addition, pectin and its derivatives have been widely used for encapsulating and delivering functional ingredients in pharmaceuticals and foods to enhance their bioactivity.

[0005] As a hydrophilic macromolecular polysaccharide, emulsification is one of the important functional properties of pectin. It adsorbs onto the surface of oil droplets through hydrophobic substances on its side chains, while the neutral sugar side chains and main chain extend into the aqueous phase, providing steric hindrance and electrostatic repulsion to prevent oil droplet aggregation and maintain the stability of the oil-water interface. Meanwhile, protein is one of the important functional groups in pectin, and its content varies depending on the origin of the raw material, extraction method, and conditions, typically accounting for 2-9% of the pectin. In pectin-based emulsions, protein, as a hydrophobic component, provides adsorption anchors for oil droplets. Furthermore, the degree of acetylation and methylation in pectin molecules also significantly affects the stability of the emulsion. With the increasing multi-scenario applications of pectin, the original structure of natural pectin often cannot directly meet the diverse functional requirements.

[0006] Based on this, many studies, while exploring the mechanism of intermolecular interactions in pectin, have adopted chemical methods or enzymatic techniques such as alkylation, amidation, quaternization, thiolation, and sulfation to intervene and enhance its emulsifying properties.

[0007] While these methods have made some progress in optimizing the functional properties of pectin, limitations remain. For example, chemical methods may introduce harmful substances, affecting the safety of pectin; enzymatic methods have harsh reaction conditions, making large-scale production difficult. Therefore, there is an urgent need to explore and develop an efficient, safe, and environmentally friendly method for pectin modification to enhance its emulsifying properties and meet its practical application needs in the food and related fields.

[0008] On April 24, 2025, a search was conducted in the China Patent Publication Database using "electrolysis and pectin and modification and isothermal and emulsification and high efficiency and bilayer" as the keywords for the full text, with the option to allow synonym expansion. No relevant literature was found.

[0009] On April 24, 2025, a search was conducted in the China Patent Publication Database using "emulsification and (electrochemistry or electrolysis)" as the title keyword and with the option to allow synonym expansion. The search revealed that the relevant existing technologies all use electrolysis to decompose the emulsion, which provides a reverse inspiration for this patent, but there is no inspiration for enhancing the emulsifying properties of pectin.

[0010] CN101896228A relates to a multiphase personal care composition. The multiphase personal care composition comprises an aqueous structured surfactant phase, a structured system, and a beneficial phase. The aqueous structured surfactant phase comprises about 5% to about 16% by weight of the multiphase personal care composition a foaming surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, or mixtures thereof, and the structured system. The structured system comprises a nonionic emulsifier with an HLB value of about 1.4 to about 1.3, about 0.05% to about 5% by weight of the multiphase personal care composition an associating polymer, and an electrolyte. The beneficial phase comprises about 5% to about 30% by weight of the multiphase personal care composition a hydrophobic beneficial substance.

[0011] CN101811756A discloses an indirect electrochemical oxidation method for treating waste emulsion. The method involves electrolyzing an electrolyte solution in an electrolytic reactor to generate acidic oxidizing potential water and alkaline reducing water. The acidic oxidizing potential water is then mixed with the waste emulsion and reacted completely to form an oil layer and a water layer. The oil and water layers are separated, and the water layer is neutralized with the alkaline reducing water before being discharged. The ratio of the acidic oxidizing potential water to the waste emulsion is 0.01–0.08 mmol / gCOD, based on the ratio of the total moles of oxidizing substances in the acidic oxidizing potential water to the total COD of the waste emulsion. The waste emulsion is used waste metal cutting fluid with a COD < 50000 mg / L. This invention utilizes electrolysis of the electrolyte solution to simultaneously generate an acidic electrolyte containing oxidizing substances, which simultaneously acidifies and breaks up the emulsion and oxidizes dissolved organic matter in the waste emulsion. After neutralization with alkaline reducing water, the pH of the water layer is between 6 and 7, allowing the neutralized water to proceed to subsequent biochemical treatment.

[0012] CN207361965U discloses an emulsion electrolyzer, wherein an overflow port is provided on the right side of the electrolyzer, and a solenoid valve is provided on the overflow port to facilitate the timely discharge of floating oil droplets. A filtration pipe is provided with a filtration hole to facilitate the effective removal of residues from the bottom of the tank. A spiral blade is provided on the stirring shaft, and the spiral blade is located at the upper end of the stirring blade to effectively regulate water quality. A dosing hopper is provided above the dosing tank, and a hopper lid is hinged to one end of the dosing hopper to prevent liquid evaporation and splashing. This emulsion electrolyzer has the advantages of good treatment effect and high efficiency, and has broad market prospects.

[0013] CN101811756B discloses an indirect electrochemical oxidation method for treating waste emulsion. The method involves electrolyzing an electrolyte solution in an electrolytic reactor to generate acidic oxidizing potential water and alkaline reducing water. The acidic oxidizing potential water is then mixed with the waste emulsion and reacted completely to form an oil layer and a water layer. The oil and water layers are separated, and the water layer is neutralized with the alkaline reducing water before being discharged. The ratio of the acidic oxidizing potential water to the waste emulsion is 0.01–0.08 mmol / gCOD, based on the ratio of the total moles of oxidizing substances in the acidic oxidizing potential water to the total COD of the waste emulsion. The waste emulsion is used waste metal cutting fluid with a COD < 50000 mg / L. This invention utilizes electrolysis of the electrolyte solution to simultaneously generate an acidic electrolyte containing oxidizing substances, which simultaneously acidifies and breaks up the emulsion and oxidizes dissolved organic matter in the waste emulsion. Furthermore, after neutralization with alkaline reducing water, the pH of the water layer is between 6 and 7, allowing the neutralized water to proceed to subsequent biochemical treatment.

[0014] CN119912028A discloses a method for electrochemical oxidation degradation of aqueous polyacrylic acid emulsion, comprising the following steps: S1, electrode preparation: graphite sheet is bonded to PTFE resin to prepare a graphite sheet electrode, then the graphite sheet electrode is immersed in Fe solution, removed after immersion, and carbonized under heating to obtain a modified graphite sheet electrode, which serves as the anode electrode; another graphite sheet electrode is directly carbonized under heating to obtain a cathode electrode; S2, the polyacrylic acid emulsion to be treated is added to an electrolyte, and sodium sulfate is added; S3, using a two-electrode system, the modified graphite sheet electrode prepared in step S1 is used as the cathode and inserted into the electrolyte of step S2 for electrochemical oxidation treatment to degrade the polyacrylic acid emulsion in the electrolyte. The method provided by this invention can efficiently degrade polyacrylic acid, and through electrode performance optimization, it has good current efficiency. The process is simple and environmentally friendly, and has good application prospects.

[0015] CN104437147B relates to the field of battery production and solves the problem of clumping and deposition during the emulsification of thickeners in lead-acid battery gel electrolytes. A method for emulsifying thickeners in lead-acid battery gel electrolytes is provided, which involves heating in a container, stirring with a stirrer, scraping the bottom wall of the container with a wall-scraping blade, and shearing with a stationary cavity fitted onto the stirrer shaft and shearing blades connected to the stirrer shaft within the stationary cavity. An emulsification apparatus includes a container, a stirrer, wall-scraping blades, and a stationary cavity. The stirrer includes a shaft and several stirring blades mounted on the shaft and located within the container. The wall-scraping blades are fitted against the inner surface of the container's bottom wall. The shaft extends vertically. The stationary cavity is fitted onto the shaft, and shearing blades are connected to the shaft and located within the stationary cavity. A connecting hole is provided on the wall of the stationary cavity, and the stirring blades are located outside the stationary cavity.

[0016] CN202988811U discloses an electrolytic flotation device for treating emulsified wastewater. It comprises a wastewater treatment tank, a controller, an A / D converter, a power supply, bipolar-connected electrolytic electrodes positioned in the bubble generation zone, and a reference electrode for measuring the potential difference between the electrolytic electrodes. The reference electrode transmits the measured voltage difference between the electrolytic electrodes to the controller. The wastewater treatment tank is equipped with an inlet, an outlet, and a level regulator for monitoring the water level. A partition divides the wastewater treatment tank into a bubble generation zone, a sedimentation zone, and a scum collection zone. A sediment outlet is located in the sedimentation zone, and a scum outlet is located in the scum collection zone, both situated outside the wastewater treatment tank. The advantages of this invention are: small and compact unit, saving land; high separation efficiency; no secondary pollution; fewer power devices; convenient maintenance; low maintenance and operating costs; high wastewater treatment efficiency; and high-density online automatic measurement and feedback control, enabling unattended operation of the device.

[0017] CN206502645U discloses an electrochemical separation reactor for oily emulsion wastewater, comprising a reactor body, a mixing device located inside the reactor body, a demulsifier supply device and a wastewater supply device connected to the reactor body via pipelines. The reactor body contains an electrode device and a filtration device, with the filtration device located below the electrode device and the mixing device above the electrode device. A drive motor is mounted on the top of the reactor body. The top of the mixing device penetrates the reactor body and is connected to the output end of the drive motor. A drain pipe penetrating the side wall of the reactor body is connected below the filtration device, and a turbidity detector is installed at this connection. The drain pipe has two outlet pipes, each equipped with a direct discharge solenoid valve and a recovery solenoid valve. This invention has a reasonable structure, is simple to operate, convenient to use, and exhibits high wastewater treatment efficiency and good results, making it highly valuable for widespread application.

[0018] CN201793449U relates to a combined electrolysis device for treating emulsified oil wastewater, comprising an electrocoagulation device and an electroflotation device. The electrocoagulation device has several electrode groups evenly distributed from top to bottom inside, each electrode group including a first electrode and a second electrode. The first and second electrode plates are respectively disposed on the left and right inner walls of the electrocoagulation device. A first inlet is located at the bottom of the electrocoagulation device, and a first outlet is located at the top. The electroflotation device has an electrode tank inside, with several third electrode plates vertically distributed from left to right inside the tank. A second inlet is located at the bottom of the electroflotation device, connected to the first outlet of the electrocoagulation device via a pipeline. The beneficial effects of this invention are: reducing the possibility of electrode passivation and electrode consumption in the electrocoagulation device, while improving the oxidizing properties of the treatment process; generating a large number of microbubbles, resulting in a separation effect superior to other air flotation methods. This equipment is unaffected by the quality of the raw water, is simple to operate, has low operating costs, and provides good treatment results.

[0019] CN1321905C describes a method for treating marine emulsified oil wastewater using a combination of oxidation electrolysis and particle swarm electrolysis in the field of environmental protection technology. The method involves electrolyzing the emulsified oil particles, which carry a negative charge. During electrolysis, this negative charge is neutralized on the anode surface, causing demulsification and oil accumulation. Small oil droplets coalesce into larger droplets that float upwards to the top of the electrolytic cell. The anode used in the electrolysis employs an insoluble electrode with oxygen evolution function. This type of anode neutralizes the negative charge of the emulsified oil particles and simultaneously generates hydroxyl radicals (OH) that act on the emulsified oil particles, accelerating the demulsification reaction without producing solid precipitates. The water treated by the insoluble electrode electrolysis is then treated by particle swarm electrolysis before being discharged. This invention is applicable to the treatment of emulsified oil wastewater in marine oily wastewater, offering good treatment results, long electrode lifespan, no secondary pollution, and low cost, thus possessing broad application potential.

[0020] CN217202373U discloses an electrolytic flotation device for emulsified oil wastewater, comprising a wastewater inlet pipe, a coagulant inlet pipe, a coagulation tank, a mixer, a sedimentation tank, a filter screen, a sewage pump, a sewage pipe, a stilling tank, a connecting pipe, a connecting pipe valve, the main body of the electrolytic flotation device, a slag discharge pipe, and a drainage pipe. The wastewater inlet pipe and the coagulant inlet pipe are located above the coagulation tank. The mixer is fixed inside the coagulation tank. The sedimentation tank is located below the coagulation tank. A sewage pump is located at the bottom of the sedimentation tank and connected to the sewage pipe. The stilling tank and the coagulation tank are connected by a filter screen. A connecting pipe is located on one side of the stilling tank, and the other side of the connecting pipe is connected to the main body of the electrolytic flotation device. A connecting pipe valve is located on the connecting pipe. A slag discharge pipe and a drainage pipe are located on one side of the main body of the electrolytic flotation device. By setting up a coagulation tank, the wastewater and coagulant are fully mixed under the action of the mixer, and pre-treated in the coagulation tank. Large impurities are filtered out by the filter screen, thereby shortening the wastewater treatment time.

[0021] CN1765761A discloses a method for treating marine emulsified oil wastewater using a combination of oxidation electrolysis and particle cluster electrolysis in the field of environmental protection technology. The method involves electrolyzing the emulsified oil, where the emulsified oil particles carry a negative charge. During electrolysis, this negative charge is neutralized on the anode surface, causing demulsification and oil accumulation. Small oil droplets coalesce into larger droplets that float upwards to the top of the electrolytic cell. The anode used in the electrolysis employs an insoluble electrode with oxygen-evolving capabilities. This type of anode neutralizes the negative charge of the emulsified oil particles during electrolysis and simultaneously generates hydroxyl radicals (OH·) that act on the emulsified oil particles, accelerating the demulsification reaction without producing solid precipitates. The water treated by the insoluble electrode electrolysis is then treated by particle cluster electrolysis before being discharged. This invention is applicable to the treatment of emulsified oil wastewater from marine oily wastewater, offering good treatment results, long electrode lifespan, no secondary pollution, and low cost, thus possessing broad application potential.

[0022] CN120943465A belongs to the field of water treatment and oily wastewater reuse technology, proposing an electrochemical-based process for treating high-oil-content emulsified wastewater. The oily wastewater enters a pretreatment unit, where it undergoes filtration, flotation, and pH adjustment to remove floating oil and suspended matter, and to adjust the pH to a suitable range. The reacted oily wastewater then enters an electrochemical device where a suitable voltage is applied to the electrodes to destabilize the emulsified oil, thus achieving demulsification. The wastewater then enters an oil-water separation device, where the demulsified oil droplets coalesce, grow, and float to the surface, yielding recoverable oil at the top. After a prolonged period of operation, the wastewater enters a regeneration unit to restore the electrochemical demulsification unit to its optimal demulsification and oil removal efficiency. This invention can treat various high-oil-content emulsified wastewaters and recover oil through voltage regulation, and is applicable to electro-desalination wastewater, machining wastewater, cold rolling wastewater, etc.

[0023] CN204454702U discloses a high-efficiency micro-electrolysis deemulsification device. This device includes a tank with an outlet and an inlet at the top and bottom, respectively, and a water distribution unit, a high-efficiency carrier unit, and a clean water collection unit arranged sequentially from bottom to top within the tank. A support layer is provided between the water distribution unit and the high-efficiency carrier unit. The inlet is located on the side wall of the tank and communicates with the water distribution unit, while the outlet is located on the side wall of the tank and communicates with the clean water collection unit. This treatment device employs a novel treatment technology combining physical and micro-electrolysis. First, it utilizes the micro-electrolysis of carbon iron to create a microelectronic environment. Then, using a special technique, nano-titanium dioxide is introduced into the carrier, allowing it to generate electrons, thereby forming oxidizing substances to treat the emulsified oil. It has advantages such as high deemulsification efficiency, thorough treatment, simple operation, no secondary pollution, and low operating costs.

[0024] CN121699622A relates to a highly efficient composite emulsifier based on a hydrophilic polyelectrolyte, belonging to the field of colloid and interface chemistry. This composite emulsifier consists of a hydrophilic polyelectrolyte and an ionic surfactant, both carrying the same charge in the aqueous phase. This composite emulsifier is a highly efficient O / W type emulsifier. The effective concentration of the polyelectrolyte can be as low as 0.001 wt.% of its mass fraction in the aqueous phase, while the effective concentration of the ionic surfactant can be as low as 0.01 times its critical micelle concentration (cmc). This composite emulsifier exhibits good biocompatibility and can be safely used in food, pharmaceutical, and cosmetic fields. CN107375035B relates to a multiphase personal care composition. The multiphase personal care composition comprises an aqueous structured surfactant phase, a structured system, and a beneficial phase. The aqueous structured surfactant phase comprises about 5% to about 16% by weight of the multiphase personal care composition a foaming surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, or mixtures thereof, and a structured system. The structured system comprises a nonionic emulsifier with an HLB value of about 1.4 to about 13, about 0.05% to about 5% by weight of the multiphase personal care composition an associative polymer, and an electrolyte. The beneficial phase comprises about 5% to about 30% by weight of the multiphase personal care composition a hydrophobic beneficial substance.

[0025] CN104437147A relates to the field of battery production and solves the problem of clumping and deposition during the emulsification of thickeners in lead-acid battery gel electrolytes. A method for emulsifying thickeners in lead-acid battery gel electrolytes involves heating within a container, stirring with a stirrer, scraping the bottom wall of the container with a wall-scraping blade, and shearing with a stationary cavity fitted onto the stirrer shaft within the container and shearing blades connected to the stirrer shaft within the stationary cavity. An emulsification apparatus includes a container, a stirrer, wall-scraping blades, and a stationary cavity. The stirrer includes a shaft and several stirring blades mounted on the shaft and located within the container. The wall-scraping blades are fitted against the inner surface of the container's bottom wall. The shaft extends vertically. The stationary cavity is fitted onto the shaft, and shearing blades are connected to the shaft and located within the stationary cavity. A connecting hole is provided on the wall of the stationary cavity, and the stirring blades are located outside the stationary cavity.

[0026] CN201179363Y discloses an electrochemical separation reactor for oily emulsion wastewater. The reactor body is connected to a wastewater inlet pipe and a treated effluent pipe. The reactor body is characterized by: an electrode unit for electrochemical reaction is provided within the reactor body; the two electrodes of the electrode unit are respectively connected to the two power output terminals of a dedicated electrode power supply; a sampling port and an online monitoring instrument interface are installed approximately 50 mm below the electrode unit; a dosing unit is provided outside the reactor body, comprising a wastewater and demulsifier mixing unit, and the dosing unit's water supply pipe is connected to the wastewater inlet pipe of the reactor body.

[0027] CN107375035A relates to a multiphase personal care composition. The multiphase personal care composition comprises an aqueous structured surfactant phase, a structured system, and a beneficial phase. The aqueous structured surfactant phase comprises about 5% to about 16% by weight of a foaming surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, or mixtures thereof, and the structured system. The structured system comprises a nonionic emulsifier with an HLB value of about 1.4 to about 13, about 0.05% to about 5% by weight of an associating polymer, and an electrolyte. The beneficial phase comprises about 5% to about 30% by weight of a hydrophobic beneficial substance.

[0028] CN205710017U relates to a special electrolytic flocculation device for oily emulsion wastewater, comprising an inlet, a primary electrolytic cell, a secondary electrolytic cell, a tertiary electrolytic cell, a slag scraper, a scum outlet, and a clear liquid outlet. Each electrolytic cell is isolated from the others by polypropylene material. Each stage of the electrolytic cell has a drain outlet at its lower part. The slag scraper is located above the primary, secondary, and tertiary electrolytic cells and is used to treat the solid waste generated by the flocculation and flotation process, which is discharged through the scum outlet. The treated, compliant clear water is discharged through the clear liquid outlet.

[0029] CN1844473A discloses a novel method for preparing ultrafine metal powders with controllable particle size—an electrolytic emulsification method. This method can prepare a series of ultrafine metal powders with controllable particle size and good dispersibility, ranging from tens of nanometers to micrometers. This process has advantages such as simple equipment, low production cost, no environmental pollution, high yield, high efficiency, and the finished powder is durable for storage and transportation, easy to store, and has low environmental requirements, making it suitable for industrial production. The method has the following characteristics: First, an emulsion precursor solution for the electrochemical reaction is prepared using an electromagnetic stirring ultrasonic mixing tank; second, the emulsion precursor solution is injected into each electrolytic cell of the ultrafine powder preparation workstation, using the target powder metal material as the anode and a mesh electrode as the cathode. The pH value of the solution is adjusted using an acid corresponding to the electrolyte anion. Under the action of an applied electric field, electrodeposition occurs on the sacrificial anode, causing the generated powder to loosely adhere to the cathode surface; finally, the powder is desorbed, washed, dehydrated, vacuum dried, and packaged. The method of this invention can be used to produce ultrafine metal powder materials of various types, such as copper, silver, zinc, iron, and nickel. Summary of the Invention

[0030] Purpose of the invention: To provide a more effective method and equipment for shortening the preparation cycle and synergistically regulating interfacial tension in the electrochemical modification and emulsification of pectin. Specific objectives are detailed in the specific implementation section, which outlines several substantial technical effects.

[0031] To achieve the above objectives, the present invention adopts the following technical solution: A pectin electrochemical modification and emulsification enhancement method for shortening the preparation cycle and synergistically regulating interfacial tension, characterized in that... The method includes the following steps: Step 1: Disperse pectin in the reaction medium and hydrate it, stirring until homogeneous to obtain a pectin solution; Step 2: Pour the pectin solution into the electrochemical reaction tank, turn on the magnetic stirrer, and use the temperature control system to adjust and maintain the pectin solution at the set temperature; then turn on the power to start the anode and cathode; the pectin structure is reshaped in a synergistic manner using electric and temperature fields: the charge density is enhanced through electrochemical polarization and redox effects, the molecular weight and conformational evolution are controlled by precise temperature control, and the conformational rearrangement of endogenous proteins is induced by electric field force, thereby synergistically enhancing its emulsifying properties and stability in the dimensions of electrostatic shielding, steric hindrance, and interfacial rheology; after the reaction is completed, the modified material is taken out; Step 3: The modified material is subjected to alcohol precipitation and drying to obtain structure-modified pectin.

[0032] A further technical solution of the present invention is that, in step two: the pectin conformation is reshaped in a synergistic manner by electric field and temperature field, and endogenous protein conformational rearrangement is induced by electrochemical polarization to expose hydrophobic groups, thereby significantly enhancing emulsification performance from the dimensions of electrostatic shielding and interfacial rheology.

[0033] A further technical solution of the present invention is that the reaction medium is a 0.5-10% (v / v) aqueous ethanol solution, and the dilution water is selected from at least one of distilled water, tap water or deionized water; The concentration of the pectin solution is 1-5% (w / w), and the dispersion and hydration time is 10-20 h; The temperature of the electrochemical cell was kept constant at 0–30 °C during the electrochemical modification process; The electrochemical modification voltage ranges from 10 to 1000 V, and the reaction time ranges from 10 to 60 min.

[0034] A further technical solution of the present invention is that, in step three: 75-100% (v / v) ethanol is added to the modified material, and the mixture is centrifuged at 5000-18000 rpm for 5-25 min; then dried at 40-75℃ to obtain the structure-modified pectin.

[0035] A further technical solution of the present invention is that, in step two: the anode electrode and the cathode electrode are both metal platinum sheets, and the rotation speed of the magnetic stirrer in the electrochemical reaction cell is 100-500 rpm.

[0036] A further technical solution of the present invention is that, by utilizing electrochemical polarization and redox effects, the charge density of molecules is effectively enhanced, and the electrostatic repulsion between droplets is significantly improved; at the same time, by precisely controlling the molecular weight and conformation through temperature control, the hydrophilic-hydrophobic balance is optimized, so that the modified pectin has a faster adsorption rate and lower interfacial tension at the oil-water interface.

[0037] By inducing conformational rearrangement of pectin endogenous proteins using an electric field, hydrophobic groups are fully exposed, thereby constructing a high-strength interfacial film. This synergistic enhancement from three dimensions—electrostatic shielding, steric hindrance, and interfacial rheology—enables the generated emulsion to exhibit superior stability in complex environments, effectively preventing droplet aggregation and separation.

[0038] A pectin electrochemical modification emulsification enhancement device for shortening the preparation cycle and synergistically regulating interfacial tension, characterized in that it is used to achieve the method described above. The electrochemical modification device is a dedicated electrochemical modification device; Its structure is as follows: The device includes an electrode holder 1), the electrode holder includes a holder top 2) and a holder bottom 4), and also includes a holder connecting rod 3), the holder top 2) and the holder bottom 4) are connected by uniformly distributed holder connecting rods 3), the surface of the holder connecting rod 3) includes a set of symmetrical grooves for accommodating the protrusions 13 of the platinum sheet electrode 5), and the holder bottom 4) is provided with a ring of annular limiting grooves for fixing the bottom end of the electrode; Insert the platinum sheet electrode 5) symmetrically into the electrode holder 1), insert and remove the electrode using the metal pull ring 6) at the top of the electrode, and install or remove the electrode holder 1) using the holder handle 7). Place the electrode holder 1) with the platinum electrode 5 inserted into it into the cylindrical double-layer water bath sealed electrochemical cell 8), with the electrode holder 1 tightly attached to the inner wall of the electrochemical cell 8). The cylindrical double-layer water bath sealed electrochemical cell 8) is connected to the inlet 9) and the outlet 10). The space between the electrochemical cell 8) and the electrode holder 1) is the water bath space 11. The temperature of the pectin solution can be controlled by pumping in cooling circulating water into the water bath space. The magnetic stir bar 12) is placed in the cylindrical double-layer water bath sealed electrochemical cell 8) to make the temperature of the pectin solution uniformly distributed; The supporting device can achieve flexible insertion and removal of electrodes and expansion of the number of electrodes through a fixing frame with symmetrical cuboid grooves and metal pull rings; the electrochemical cell adopts a "bottom in, top out" double-layer sealed water bath structure, combined with magnetic stirring to ensure uniform field distribution, which can effectively avoid polysaccharide degradation caused by local overheating.

[0039] A further technical solution of the present invention is that, before the electrochemical modification begins, the number of platinum sheet electrodes 5) on the electrode holder 1) is adjusted; After the electrochemical modification is completed, pull up the handle 7 of the fixing bracket to facilitate the quick removal of the electrode fixing bracket 1); then pull up the metal pull ring 6) to quickly disassemble the platinum electrode 5).

[0040] A further technical solution of the present invention is that the bottom of the electrochemical cell 8) includes an outlet, the outlet includes a valve, and the outlet can discharge the electrochemically modified liquid.

[0041] A pectin electrochemical modification emulsification enhancement method for shortening the preparation cycle and synergistically regulating interfacial tension, characterized in that the method comprises any one of the following: A.1) Disperse 12g of orange peel pectin in 400g of distilled water containing 5% (v / v) ethanol, and stir at room temperature for 10h to fully hydrate the pectin and obtain a pectin solution with uniform concentration. 2) Insert the platinum sheet electrodes symmetrically into the electrode holder and connect them to the anode and cathode of the DC power supply respectively; connect the cooling circulating water device to the inlet and outlet of the 500mL cylindrical double-layer water bath sealed electrochemical cell, and then place the electrode holder with the electrodes installed into the electrochemical cell to complete the assembly of the modification device. 3) Take 300 mL of pectin solution prepared in step (1) and add it to the electrochemical modification device described in (2). Turn on the magnetic stirrer and adjust the speed to 300 rpm. Start the cooling water circulator and adjust the flow rate to 8 L / min. Adjust and keep the temperature of the pectin solution constant at 10-15℃. 4) After the temperature of the pectin solution in step (3) stabilizes, turn on the DC power supply, adjust the voltage to 200V, and react with the electric field and temperature field for 30 minutes. 5) After the reaction is complete, take out the modified material described in step (4), add 3 times the volume of 95% (v / v) ethanol to it for alcohol precipitation, centrifuge the mixture at 5000-18000 rpm for 10 min, discard the supernatant and collect the precipitated pectin. 6) Finally, place the pectin from step (5) in an electric heating drying oven and dry it at 50°C to a constant weight to obtain the structure-modified and strengthened pectin. B.1) Disperse 16g of orange peel pectin in 400g of distilled water containing 6% (v / v) ethanol, and stir at room temperature for 12h to fully hydrate the pectin and obtain a pectin solution with uniform concentration. 2) Insert two sets of platinum sheet electrodes (120mm×10mm in size) symmetrically into the electrode holder and connect them to the anode and cathode of the DC power supply respectively; connect the cooling circulating water device to the inlet and outlet of the 500mL cylindrical double-layer water bath sealed electrochemical cell, and then place the electrode holder with the electrodes installed into the electrochemical cell to complete the assembly of the modification device. 3) Take 400 mL of pectin solution prepared in step (1) and add it to the electrochemical modification device described in (2). Turn on the magnetic stirrer and adjust the speed to 200-400 rpm. Start the cooling water circulator and adjust the flow rate to 12 L / min. Adjust and keep the temperature of the pectin solution constant at 15-25℃. 4) After the temperature of the pectin solution in step (3) stabilizes, turn on the DC power supply, adjust the voltage to 300V, and react with the electric field and temperature field for 15min, 30min, 45min and 60min respectively. 5) After the reaction is complete, take out the modified material described in step (4), add 3 times the volume of 95% (v / v) ethanol to it for alcohol precipitation, centrifuge the mixture at 15000 rpm for 15 min, discard the supernatant and collect the precipitated pectin. 6) Finally, place the pectin from step (5) in an electric heating drying oven and dry it at 45°C to a constant weight to obtain the structure-modified and strengthened pectin.

[0042] The present invention, employing the above technical solution, has the following beneficial effects compared to the prior art: by utilizing electrochemical polarization and redox effects, the charge density of molecules is effectively enhanced, and the electrostatic repulsion between droplets is significantly improved; at the same time, by precisely controlling the molecular weight and conformation through temperature control, the hydrophilic-hydrophobic balance is optimized, resulting in the modified pectin having a faster adsorption rate and lower interfacial tension at the oil-water interface.

[0043] By inducing conformational rearrangement of pectin endogenous proteins using an electric field, hydrophobic groups are fully exposed, thereby constructing a high-strength interfacial film. This synergistic enhancement from three dimensions—electrostatic shielding, steric hindrance, and interfacial rheology—enables the generated emulsion to exhibit superior stability in complex environments, effectively preventing droplet aggregation and separation.

[0044] Highly efficient reaction and shortened process cycle: The synergistic field effect accelerates the directional reshaping of pectin molecules, and the modification of pectin can be completed in just 10 to 60 minutes, which is more than 75% more efficient than the traditional process.

[0045] Innovative structure, flexible and efficient configuration: The plug-in design and full-length symmetrical grooves ensure uniform electric field while supporting quick adjustment of the number of electrodes and overall assembly and disassembly via metal pull rings, greatly improving the maintenance efficiency and ease of operation of the device.

[0046] Precise temperature control and uniform field distribution: Through the double-layer water bath circulation with bottom inlet and top outlet and magnetic stirring, the temperature gradient of the reaction tank is effectively eliminated, ensuring the consistency of pectin conformation evolution, preventing local overheating that leads to molecular degradation, and significantly improving product stability.

[0047] Green and environmentally friendly, with highly controllable parameters: using ethanol-water solution as the medium, the process is clean and pollution-free; precise modification is achieved through multi-parameter synergistic regulation, and the method and device have wide applicability to polysaccharide biomacromolecules.

[0048] In summary, this invention, through an innovative electric field-temperature field synergistic modification process and a matching detachable pluggable electrode device, not only achieves precise reshaping of the pectin molecular structure and significant enhancement of emulsification performance, but also greatly improves the operational flexibility and temperature control uniformity of the electrochemical modification process, providing an efficient, environmentally friendly and highly controllable technical solution for the preparation of high-quality modified polysaccharides. Attached Figure Description

[0049] To further illustrate the present invention, the following description is provided in conjunction with the accompanying drawings: Figure 1 Schematic diagram of a pectin electrochemical separation device; Figure 2 Physicochemical parameters of pectin; Figure 3 The interfacial tension of pectin; Figure 4 Microscopic images and particle size distribution of pectin-stabilized emulsions; Figure 5 Structural diagram of the auxiliary equipment of the invention; Figure 6 for Figure 5 A partial structural diagram; Figure 7 for Figure 5 A partial structural diagram; Figure 8 This is a structural diagram of a dedicated electrochemical reaction cell. The components are: 1. Electrode holder; 2. Top of holder; 3. Connecting rod of holder; 4. Bottom of holder; 5. Platinum electrode; 6. Metal pull ring; 7. Holder of holder; 8. Cylindrical double-layer water bath sealed electrochemical cell; 9. Outlet; 10. Inlet; 11. Water bath space; 12. Magnetic stir bar; 13. Protrusion. Detailed Implementation

[0050] The present invention will be further illustrated below with reference to the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0051] The purpose of this invention is to provide a technical method for electrochemically modifying and enhancing the emulsifying properties of pectin.

[0052] By utilizing electrochemical polarization and redox effects, the charge density of molecules is effectively enhanced, significantly improving the electrostatic repulsion between droplets. At the same time, by precisely controlling the molecular weight and conformation through temperature control, the hydrophilic-hydrophobic balance is optimized, resulting in the modified pectin exhibiting a faster adsorption rate and lower interfacial tension at the oil-water interface.

[0053] By inducing conformational rearrangement of pectin endogenous proteins using an electric field, hydrophobic groups are fully exposed, thereby constructing a high-strength interfacial film. This synergistic enhancement from three dimensions—electrostatic shielding, steric hindrance, and interfacial rheology—enables the generated emulsion to exhibit superior stability in complex environments, effectively preventing droplet aggregation and separation. This method is not only widely applicable but also economical, efficient, and environmentally friendly.

[0054] To achieve the above objectives, the present invention provides a method and apparatus for electrochemically modifying and enhancing the emulsifying properties of pectin, comprising the following steps: (1) Disperse a certain amount of pectin in the reaction medium, hydrate it fully, and stir it evenly to obtain a pectin solution; (2) Insert a certain number of electrodes symmetrically into the electrode holder and connect them to the anode and cathode of the DC power supply respectively; connect the cooling circulating water device to the inlet and outlet of the 500mL cylindrical double-layer water bath sealed electrochemical cell, and then place the electrode holder with the electrodes installed into the electrochemical cell to complete the assembly of the modification device. (3) Pour the prepared pectin solution into the electrochemical reaction cell, turn on the magnetic stirrer, and use the cooling circulating water machine to adjust and keep the pectin solution at the required temperature; then turn on the power to start the anode and cathode to work; after the reaction is completed, take out the modified material from the electrochemical reaction cell. (4) The modified material was then subjected to alcohol precipitation and drying to obtain structure-modified pectin.

[0055] Further, the reaction medium in step (1) is a 0.5-10% (v / v) aqueous ethanol solution.

[0056] Further, the water used in step (1) for the reaction medium is selected from at least one of distilled water, tap water or deionized water.

[0057] Furthermore, in step (1), the concentration of the pectin solution is 1-5% (w / w), and the dispersion and hydration time is 10-20h.

[0058] Furthermore, in step (2), both the anode and cathode electrodes are made of platinum metal sheets, and the number of anode and cathode electrodes is 1 to 15 sets.

[0059] Furthermore, in step (3), the rotation speed of the magnetic stirrer in the electrochemical reaction cell is 100 to 500 rpm.

[0060] Furthermore, during the electrochemical modification process in step (3), the temperature of the electrochemical cell is kept constant at 0–30°C, and the flow rate of the cooling circulating water machine is 5–20 L / min.

[0061] Furthermore, in step (3), the electrochemical modification voltage is 10–1000 V and the reaction time is 10–60 min.

[0062] Further, in step (4), 3 times the volume of 75-100% (v / v) ethanol is added to the modified material, and the mixture is centrifuged at 5000-18000 rpm for 5-25 min.

[0063] Further, the modified material in step (4) is dried at 40-75°C until the moisture content is constant and meets the national standard requirements, thus obtaining the structure-modified pectin.

[0064] The beneficial effects of this invention are: Highly efficient reaction and shortened process cycle: The synergistic field effect accelerates the directional reshaping of pectin molecules, and the modification of pectin can be completed in just 10 to 60 minutes, which is more than 75% more efficient than the traditional process.

[0065] Innovative structure, flexible and efficient configuration: The plug-in design and full-length symmetrical grooves ensure uniform electric field while supporting quick adjustment of the number of electrodes and overall assembly and disassembly via metal pull rings, greatly improving the maintenance efficiency and ease of operation of the device.

[0066] Precise temperature control and uniform field distribution: Through the double-layer water bath circulation with bottom inlet and top outlet and magnetic stirring, the temperature gradient of the reaction tank is effectively eliminated, ensuring the consistency of pectin conformation evolution, preventing local overheating that leads to molecular degradation, and significantly improving product stability.

[0067] Green and environmentally friendly, with highly controllable parameters: using ethanol-water solution as the medium, the process is clean and pollution-free; precise modification is achieved through multi-parameter synergistic regulation, and the method and device have wide applicability to polysaccharide biomacromolecules.

[0068] In summary, this invention, through an innovative electric field-temperature field synergistic modification process and a matching detachable pluggable electrode device, not only achieves precise reshaping of the pectin molecular structure and significant enhancement of emulsification performance, but also greatly improves the operational flexibility and temperature control uniformity of the electrochemical modification process, providing an efficient, environmentally friendly and highly controllable technical solution for the preparation of high-quality modified polysaccharides. Example

[0069] (1) Disperse 12g of orange peel pectin in 400g of distilled water containing 5% (v / v) ethanol and stir at room temperature for 10h to fully hydrate the pectin and obtain a pectin solution with uniform concentration. (2) Insert a pair of platinum sheet electrodes symmetrically into the electrode holder and connect them to the anode and cathode of the DC power supply respectively; connect the cooling circulating water device to the inlet and outlet of the 500mL cylindrical double-layer water bath sealed electrochemical cell, and then place the electrode holder with the electrodes installed into the electrochemical cell to complete the assembly of the modification device. (3) Take 300 mL of pectin solution prepared in step (1) and add it to the electrochemical modification device described in (2). Turn on the magnetic stirrer and adjust the speed to 300 rpm. Start the cooling water circulator and adjust the flow rate to 8 L / min. Adjust and keep the temperature of the pectin solution constant at 15℃. (4) After the temperature of the pectin solution in step (3) stabilizes, turn on the DC power supply, adjust the voltage to 200V, and react with the electric field and temperature field for 30 minutes. (5) After the reaction is complete, take out the modified product described in step (4), add 3 times the volume of 95% (v / v) ethanol to it for alcohol precipitation, centrifuge the mixture at 12000 rpm for 10 min, discard the supernatant and collect the precipitated pectin. (6) Finally, place the pectin from step (5) in an electric heating drying oven and dry it at 50°C to constant weight to obtain the structure-modified and strengthened pectin. Example

[0070] (1) Disperse 16g of orange peel pectin in 400g of distilled water containing 6% (v / v) ethanol and stir at room temperature for 12h to fully hydrate the pectin and obtain a pectin solution with uniform concentration. (2) Insert two sets of platinum sheet electrodes (120mm×10mm in size) symmetrically into the electrode holder and connect them to the anode and cathode of the DC power supply respectively; connect the cooling circulating water device to the inlet and outlet of the 500mL cylindrical double-layer water bath sealed electrochemical cell, and then place the electrode holder with the electrodes installed into the electrochemical cell to complete the assembly of the modification device. (3) Take 400 mL of pectin solution prepared in step (1) and add it to the electrochemical modification device described in (2). Turn on the magnetic stirrer and adjust the speed to 350 rpm. Start the cooling water circulator and adjust the flow rate to 12 L / min. Adjust and keep the temperature of the pectin solution constant at 20℃. (4) After the temperature of the pectin solution in step (3) stabilizes, turn on the DC power supply, adjust the voltage to 300V, and react with the electric field and temperature field for 15 minutes. (5) After the reaction is complete, take out the modified product described in step (4), add 3 times the volume of 95% (v / v) ethanol to it for alcohol precipitation, centrifuge the mixture at 15000 rpm for 15 min, discard the supernatant and collect the precipitated pectin. (6) Finally, place the pectin from step (5) in an electric heating drying oven and dry it at 45°C to constant weight to obtain the structure-modified and strengthened pectin. Example

[0071] It is basically the same as Example 2, except that the time for the electric field and temperature field to react in step (4) is 30 min. Example

[0072] It is basically the same as Example 2, except that the time for the electric field and temperature field to react in step (4) is 45 min. Example

[0073] It is basically the same as Example 2, except that the time for the electric field and temperature field to react in step (4) is 60 min.

[0074] Comparative Example 1 This comparative example uses raw materials from the same source as those in Example 1, but without any electrochemical structural modification, and is directly used as a control group for subsequent performance testing.

[0075] Experimental Example 1 - Determination of Weight-Average Molecular Weight The molecular weight (Mw) of pectin was analyzed and calculated using an HPGPC system. The mobile phase was 100 mmol / L sodium nitrate (containing 0.04% NaN3), the flow rate was 0.6 mL / min, and the column temperature was 35 °C for isocratic elution. Pectin samples were prepared into 1 mg / mL solutions using the mobile phase. Separation was performed using an Ultrahydrogel Guard guard column in series with Ultrahydrogel 2000 and 1000 columns, and the samples were detected using a 2414 differential refractive index detector. Eight dextran standards (Mw: 1 × 10⁻⁶) were used. 3 ~1×10 7 The pectin was dissolved in the mobile phase to prepare a 2 mg / mL solution, filtered through a 0.45 μm filter membrane, and then analyzed by a liquid chromatography system. The obtained data were processed using Breeze data processing software to establish a standard curve. Subsequently, the differential elution curve of the obtained pectin sample was integrated based on the standard curve to obtain the molecular weight of the corresponding pectin.

[0076] Experimental Example 2 - Determination of Galacturonic Acid Content The galacturonic acid content in pectin was determined colorimetrically using 3-phenylphenol as the colorimetric reagent. After color development, the maximum absorbance at 520 nm was measured using a UV-Vis spectrophotometer. A standard curve was established using D-galacturonic acid as the standard, and the galacturonic acid content in pectin was calculated using the standard curve.

[0077] Experimental Example 3 - Determination of the degree of methyl esterification and acetylation The degree of methyl esterification and acetylation of pectin was determined by HPLC. 30 mg of pectin sample was saponified in 1 mL of a saponification solution containing 0.4 M NaOH (isopropanol:water = 1:1, v / v) at 25 °C for 2 h. The resulting saponified solution was then filtered through a 0.45 μm filter and analyzed by HPLC. The chromatographic system used 5 mmol / L H₂SO₄ as the mobile phase with isocratic elution at a flow rate of 0.6 mL / min, a column temperature of 45 °C, and an injection volume of 25 μL. A 2414 differential refractive index detector was used for sample detection. The degree of methyl esterification and acetylation in this experiment was obtained by calculating the molar ratio of methanol to acetic acid to galacturonic acid after saponification.

[0078] Experimental Example 4 - Determination of Monosaccharide Composition 20 mg of pectin was placed in a digestion tube containing 2 mL of viscozyme-L pectinase and treated at 45 °C for 12 h. Then, 1 mL of trifluoroacetic acid (4 M) was added, and the mixture was heated in an oil bath (110 °C) for 2 h to fully hydrolyze the pectin sample. Next, 2 mL of ammonia was added to the cooled solution in the tube, and the volume was adjusted to 100 mL with distilled water. After filtration through a 0.45 μm aqueous membrane, 25 μL of the hydrolysate was injected into an HPAEC system equipped with a CarboPac PA1 analytical column (250 × 4 mm) at a flow rate of 1 mL / min and a temperature of 30 °C. The monosaccharide content in the sample was determined using a standard curve plotted for rhamnose (Rha), arabinose (Ara), galactose (Gal), glucose (Glc), and xylose (Xyl).

[0079] Experimental Example 5 - Preparation of Emulsion 0.5g of pectin was dispersed in 44.5g of distilled water and magnetically stirred overnight to ensure full hydration. The pH was then adjusted to 3.8 using 0.5M NaOH / HCl solution, followed by mixing with 5g of camellia seed oil. The mixture was pre-homogenized for 2 minutes at 20,000 rpm using an IKA T25 high-speed shear mill to obtain a crude emulsion. Finally, the crude emulsion was homogenized for two cycles at 50 MPa using a NANO high-pressure homogenizer to obtain a fresh emulsion.

[0080] Experimental Example 6 - Determination of Interfacial Tension The interfacial tension of pectin at the oil-water interface was determined using the pendant drop method with an OCA40 Micro surface tension and contact angle meter. A 12 μL solution of 1% (w / w) pectin was suspended in medium-chain fatty acids, and the droplet morphology was recorded for 20 min using high-speed imaging. The interfacial tension was calculated using SCA-20 software based on the Young–Laplace equation. All measurements were performed at 25 °C.

[0081] Experimental Example 7 - Determination of Emulsion Particle Size The droplet properties of the emulsion were evaluated using a Malvern MasterSizer 3000 laser particle size analyzer. The refractive indices of distilled water and MCT were 1.33 and 1.45, respectively. The volume average particle size (d) was used as the metric. 4,3 =Σn i d i 4 / Σn i d i 3 , where n i Indicates a diameter of d i The average droplet size is represented by the number of particles.

[0082] In summary, the beneficial effects of the electrochemical modification method and apparatus for enhancing pectin emulsification disclosed in this invention have been significantly verified through experimental data: [The text abruptly ends here, likely due to an incomplete sentence or missing information.] Figure 2 It is evident that the electrochemical modification method disclosed in this invention, through precise temperature and electrical synergistic control, minimizes the degradation and damage of pectin molecules by physicochemical factors, successfully preserving the integrity of the pectin skeleton structure and avoiding the side effects of traditional strong chemical modification; Figure 3 It can be seen that this method significantly improves the interfacial activity of pectin. The modified pectin exhibits a faster adsorption rate at the oil-water interface, and the equilibrium interfacial tension at 20 min is significantly reduced from 19.70 mN / m of the original pectin (Comparative Example 1) to a minimum of 9.19 mN / m (Example 4), a reduction of 53.4%. This is attributed to the conformational rearrangement of pectin endogenous proteins induced by the electric field, which fully exposes its hydrophobic groups and allows them to be directionally adsorbed at the interface; Figure 4 It is evident that the structure-modified pectin prepared using this method exhibits excellent emulsifying properties. Taking tea oil emulsion as an example, its average particle size was significantly reduced from 2.14 μm in the original pectin to 1.93–1.16 μm. This substantial reduction in particle size signifies an increase in the strength of the interfacial adsorption film and enhanced emulsion stability. This modification technique, which achieves a significant performance leap while maintaining the integrity of the molecular structure, greatly enhances the application potential and commercial value of pectin as a natural emulsifier and stabilizer in high-end foods, delivery systems, and pharmaceutical preparations.

[0083] It is important to note that this patent provides a dedicated device: It boasts the following unique advantages: 1. The pluggable groove and metal pull ring design enable dynamic and precise adjustment of the number and spacing of electrodes; 2. The dual-layer circulating water bath structure combined with magnetic stirring ensures real-time and precise temperature control of the reaction system, effectively preventing pectin thermal degradation; 3. The integrated handle design allows for quick assembly and disassembly of the electrode assembly, significantly improving experimental efficiency and maintenance convenience; 4. The standardized physical structure ensures the stability of the temperature-electricity synergistic environment, guaranteeing a high degree of consistency in the quality of pectin-modified products. This greatly facilitates related research.

[0084] The device includes an electrode holder 1, which includes a top 2 and a bottom 4, and also includes a connecting rod 3. The top 2 and the bottom 4 are connected by evenly distributed connecting rods 3. The surface of the connecting rod 3 includes a set of symmetrical grooves, and the bottom 4 is provided with an annular limiting groove for fixing the bottom end of the electrode. Platinum sheet electrodes 5 are symmetrically inserted into electrode holder 1. Electrodes are inserted, removed, and expanded using the metal pull ring 6 at the top of the electrode. Electrode holder 1 is installed or removed using the holder handle 7. The electrode holder 1 with the platinum electrode 5 inserted is placed in the cylindrical double-layer water bath sealed electrochemical cell 8, with the electrode holder 1 closely attached to the inner wall of the electrochemical cell 8.

[0085] The cylindrical double-layer water bath sealed electrochemical cell 8 is connected to the inlet 9 and the outlet 10. The water bath space 11 is between the electrochemical cell 8 and the electrode fixing frame 1. The temperature of the pectin solution can be controlled by pumping in cooling circulating water into the water bath space. The magnetic stir bar 12 is placed in the cylindrical double-layer water bath sealed electrochemical cell 8 to ensure that the temperature of the pectin solution is evenly distributed.

[0086] In summary, this invention belongs to the field of natural product modification technology and discloses a method and apparatus for electrochemically modifying and enhancing the emulsifying properties of pectin. The method involves: dispersing pectin in a reaction medium to achieve full hydration and stirring until a pectin solution is obtained; pouring the prepared pectin solution into an electrochemical reaction tank, turning on a magnetic stirrer, and using a cooling circulating water system to adjust and maintain the pectin solution at the required temperature; subsequently, turning on the power supply to activate the anode and cathode; employing a synergistic combination of electric and temperature fields to directionally reshape the pectin structure, enhancing charge density through electrochemical polarization and redox effects to improve electrostatic repulsion, combining precise temperature control to regulate molecular weight and conformational evolution to optimize hydrophilicity-hydrophobicity balance and increase interfacial adsorption rate, and using electric field force to induce conformational rearrangement of endogenous proteins to expose hydrophobic groups and construct a high-strength interfacial film, thereby synergistically enhancing its emulsifying performance and stability in the dimensions of electrostatic shielding, steric hindrance, and interfacial rheology; after the reaction, removing the modified material from the electrochemical reaction tank; and then subjecting the modified material to alcohol precipitation and drying to obtain structure-modified pectin. The method provided by this invention can significantly enhance the stability of emulsions, reducing the average particle size of the emulsion from 2.14 μm of the original pectin to 1.93–1.16 μm. Compared with existing pectin modification technologies, this method is simple, efficient, energy-saving, environmentally friendly, safe, and low-cost, and can further broaden the application of pectin in the food, pharmaceutical, and chemical industries.

[0087] In summary, this invention discloses a method and apparatus for electrochemically modifying and enhancing the emulsifying properties of pectin. Experimental verification shows that the equilibrium interfacial tension of the modified pectin is significantly reduced from 19.70 mN / m to 9.19 mN / m, resulting in a decrease in the average particle size of the tea oil emulsion from 2.14 μm to 1.16 μm. The supporting apparatus utilizes a fixing frame with symmetrical cuboid grooves and metal pull rings to allow for flexible electrode insertion and removal and expansion of the electrode quantity. The electrochemical cell employs a "bottom-in, top-out" double-layer sealed water bath structure, combined with magnetic stirring to ensure uniform field distribution and effectively avoid polysaccharide degradation caused by localized overheating. This invention combines the advantages of high efficiency, environmental friendliness, and precision, providing an advanced green technology solution for the precise modification and industrial application of polysaccharide biomolecules.

[0088] 1. Example (Technical solution: pectin hydration → synergistic modification by electric field and temperature field → alcohol precipitation and drying) Compared to the shortcomings of existing technologies, such as the introduction of harmful substances in chemical modification, the harsh conditions and difficulty in scaling up enzymatic methods, the long modification cycle of traditional methods, and the insufficient emulsification and stability of pectin, this patent innovatively combines electrochemical polarization, redox effects, and precise temperature control in a non-obvious way. By synergistically reshaping the pectin structure through electric and temperature fields, it enhances molecular charge density, regulates molecular weight and conformational evolution, and induces conformational rearrangement of endogenous proteins. It synergistically improves emulsification performance and stability from the dimensions of electrostatic shielding, steric hindrance, and interfacial rheology. No harmful chemical reagents are added throughout the process, the reaction conditions are mild and easy to control, and it is suitable for large-scale production, completely solving the safety, scalability, and efficiency defects of existing modification methods.

[0089] Correspondence analysis of the attached figures Figure 1 analyze: Figure 1 The invention clearly demonstrates the complete process of the pectin electrochemical modification reaction tank, cooling water circulation machine, unmodified pectin-based tea oil emulsion and modified pectin-based tea oil emulsion. It intuitively presents the two core modification pathways of polarization oxidation and endogenous protein conformational rearrangement, which strongly proves that the present invention uses electric field-temperature field synergy to achieve directional remodeling of pectin structure and demonstrates the core viewpoints of the present invention that the modification process is controllable, green and mild and free of chemical pollution.

[0090] 2. Example (Technical solution: Electric field-temperature field synergistic conformation reshaping, inducing endogenous protein rearrangement to expose hydrophobic groups) Compared to the shortcomings of existing technologies, such as insufficient exposure of hydrophobic groups in natural pectin, weak interfacial adsorption capacity, and single-dimensional improvement of emulsification performance, this patent innovatively combines electrochemical polarization with endogenous protein conformation regulation in a non-obvious way. It directionally induces the conformational rearrangement of pectin endogenous proteins and fully exposes hydrophobic groups, while simultaneously optimizing electrostatic shielding and interfacial rheological properties. This allows pectin to be rapidly adsorbed at the oil-water interface and form a high-strength interfacial film, overcoming the inherent defects of natural pectin such as imbalance of hydrophilicity and hydrophobicity and low interfacial activity, and achieving a leapfrog improvement in emulsification performance.

[0091] Correspondence analysis of the attached figures Figure 1 analyze: Figure 1 The invention clearly labels the two key reactions of "polarization and oxidation" and "endogenous protein conformational rearrangement," visually presenting the molecular structural transformation from unmodified pectin to modified pectin. This strongly demonstrates that the invention can achieve endogenous protein conformational rearrangement through electric field force, and proves the viewpoint of the invention to enhance emulsification performance from the perspective of interfacial rheology.

[0092] 3. Examples (Technical solutions: limitations on reaction medium, concentration, temperature, voltage, and time parameters) Compared to existing technologies, which suffer from drawbacks such as uncontrollable modification parameters, susceptibility to pectin degradation, unstable product performance, and poor compatibility, this patent innovatively and non-obviously modifies 0.5~ 10% ethanol aqueous solution medium, 1 ~5% pectin concentration, 0~ 30℃ Temperature control, 10 With a voltage of ~1000V and a reaction time of 10~60min precisely matched, the green ethanol aqueous solution is used as the reaction medium to avoid contamination. The mild temperature and electric field parameters prevent the degradation of polysaccharide molecules. The strict parameter range ensures that the modification effect is stable and controllable. It can be adapted to the modification needs of pectin from different raw materials, and solves the problems of crude parameters and poor product consistency in existing technologies.

[0093] Correspondence analysis of the attached figures Figure 1 analyze: Figure 1 The precise temperature control point of 15.1℃, combined with the cooling water circulation machine structure, intuitively demonstrates the technical feature of constant temperature control from 0 to 30℃ in this invention. This strongly proves that this invention can avoid pectin degradation through precise temperature control, and demonstrates the viewpoint that the parameters of this invention are controllable and the product structure is intact.

[0094] Example (Technical solution: 3 times the volume 75-) 100% ethanol precipitation, 5000- Centrifuge at 18,000 rpm and dry at 40-75°C. Compared with the shortcomings of existing technologies, such as low efficiency in the separation and purification of modified products, residual impurities, easy damage to the structure during drying, and low product yield, this patent innovatively and non-obviously combines alcohol precipitation, high-speed centrifugation, and low-temperature constant-temperature drying. Three volumes of ethanol are used to achieve efficient precipitation of modified pectin, high-speed centrifugation quickly separates impurities from the supernatant, and gentle drying at 40~75℃ preserves the integrity of the molecular structure. While improving product purity and yield, this process avoids damage to the emulsifying activity of pectin during drying, thus solving the defects of existing purification processes, such as low efficiency and easy damage to the product.

[0095] Correspondence analysis of the attached figures Figure 1 analyze: Figure 1 The entire process from unmodified pectin to modified pectin and then to stable emulsion is fully presented, indirectly proving that the product still maintains high emulsifying activity after alcohol precipitation and drying. This strongly proves that the post-processing process of the present invention does not damage the functional structure of pectin, and demonstrates the view that the purification process of the present invention is mild and efficient.

[0096] 5. Example (Technical solution: platinum sheet electrode, magnetic stirring at 100~500 rpm) Compared to the shortcomings of existing technologies, such as electrode material easily contaminating the reaction system, uneven stirring leading to unbalanced field distribution, and excessive local reactions, this patent innovatively combines platinum sheet electrodes with precise magnetic stirring. The platinum sheet electrodes are chemically stable and do not release impurities, ensuring the purity of the reaction system. A stirring speed of 100~500rpm achieves uniform mixing of the pectin solution, eliminating local differences in concentration and field strength, allowing the electrochemical modification to proceed uniformly and gently throughout the process, and solving the problems of product performance fluctuations caused by electrode contamination and uneven reaction.

[0097] Correspondence analysis of the attached figures Figure 8 analyze: Figure 8 The structure of the magnetic stir bar 12 is clearly displayed. Combined with the double-layer water bath electrochemical cell 8, it intuitively demonstrates the design of uniform stirring and uniform temperature control, which strongly proves that the reaction system of the present invention has a uniform field distribution and demonstrates the view that the present invention has no local overheating and no molecular degradation.

[0098] 6. Implementation Examples (Technical Solutions: Enhancing Charge Density, Optimizing Hydrophilicity-Hydrophilicity Balance, and Constructing High-Strength Interfacial Films) Compared to the shortcomings of existing technologies, such as insufficient electrostatic repulsion of pectin droplets, slow interfacial adsorption rate, low interfacial film strength, and easy aggregation and separation of emulsions, this patent innovatively and non-obviously combines three-dimensional synergy of charge density enhancement, hydrophilicity-hydrophobicity balance regulation, and interfacial film construction. By enhancing the electrostatic repulsion of droplets through electrochemical polarization, optimizing the molecular hydrophilicity-hydrophobicity balance through temperature control to accelerate interfacial adsorption, and rearranging endogenous proteins to form a high-strength interfacial film, this patent comprehensively inhibits the aggregation and separation of emulsion droplets, allowing the emulsion to remain stable in complex environments and breaking through the core bottleneck of poor emulsion stability in existing technologies.

[0099] Correspondence analysis of the attached figures Figure 3 analyze: Figure 3 The pectin interfacial tension detection curve visually shows that the equilibrium interfacial tension of the modified pectin decreased from 19.70 mN / m to 9.19 mN / m, which strongly proves that the present invention significantly reduces interfacial tension and accelerates the interfacial adsorption rate, demonstrating the core concept of the present invention of optimizing hydrophilic-hydrophobic balance.

[0100] 7. Example (Technical solution: electrode holder 1, platinum sheet electrode 5, metal pull ring 6, holder handle 7, double-layer water bath electrochemical cell 8) Compared to the shortcomings of existing technologies, such as cumbersome electrode assembly and disassembly, limited quantity expansion, uneven temperature control, and localized overheating leading to polysaccharide degradation, this patent innovatively integrates a pluggable electrode holder 1, a symmetrical groove structure, a bottom-inlet, top-outlet double-layer water bath electrochemical cell 8, and a magnetic stir bar 12. The symmetrical groove of the electrode holder 1, combined with the metal pull ring 6, allows for flexible insertion and removal of platinum sheet electrodes 5 and expansion of their quantity. The holder handle 7 facilitates overall assembly and disassembly. The double-layer water bath electrochemical cell 8 adopts bottom-inlet, top-outlet circulating temperature control, combined with the magnetic stir bar 12 to eliminate temperature gradients, avoid localized overheating causing pectin degradation, and ensure uniform electric field distribution. This solves the problems of inconvenient operation, unbalanced temperature control, and easy product degradation in existing devices.

[0101] Correspondence analysis of the attached figures Figure 5 , Figure 6 , Figure 7 , Figure 8 analyze: Figure 5 The overall structure of electrode holder 1 is shown. Figure 6 , Figure 7 This demonstrates the mating structure of the platinum electrode 5 with protrusion 13 and groove. Figure 8 The invention showcases a double-layer water bath electrochemical cell 8, an inlet 10, an outlet 9, and a water bath space 11. The complete set of attached drawings fully demonstrates the device's plug-and-play expansion, bottom-inlet-top-outlet temperature control, and uniform stirring core design, powerfully proving that the device of the present invention is flexible, efficient, has precise temperature control, and provides a uniform field, thus demonstrating that the device of the present invention can avoid polysaccharide degradation.

[0102] 8. Example (Technical solution: adjustable number of electrodes, quick assembly and disassembly of electrode holder 1 and platinum electrode 5) Compared with the shortcomings of existing technologies, such as poor device adaptability, time-consuming disassembly and assembly, low maintenance efficiency, and difficulty in meeting the needs of different scales of modification, this patent innovatively combines dynamic adjustment of the number of electrodes with a quick disassembly and assembly structure. Before modification, the number of platinum sheet electrodes 5 can be adjusted as needed to adapt to different reaction scales. After the reaction, the electrode fixing frame 1 can be quickly removed through the fixing frame handle 7, and the platinum sheet electrodes 5 can be quickly disassembled through the metal pull ring 6. This greatly improves the device maintenance and operation efficiency and solves the defects of poor adaptability and cumbersome disassembly and assembly of traditional devices.

[0103] Correspondence analysis of the attached figures Figure 5 , Figure 6 analyze: Figure 5 The display stand features a handle 7 and a metal pull ring 6. Figure 6 The electrode insertion and removal structure is shown, which intuitively demonstrates the quick assembly and disassembly and the design for quantity expansion. This strongly proves that the device of the present invention is easy to operate and highly adaptable, and demonstrates the point that the device of the present invention is highly efficient and flexible.

[0104] 9. Example (Technical Solution: Electrochemical Cell 8 with a valve outlet at the bottom) Compared with the shortcomings of existing technologies, such as difficulty in discharging modified liquid, large amount of residue, easy contamination during transfer, and cumbersome operation, this patent innovatively integrates a valved discharge port into the bottom of the electrochemical cell 8 in a non-obvious way. It uses gravity to achieve rapid and complete discharge of modified liquid, reduces the risk of contamination during system residue and transfer, simplifies the discharge operation process, and solves the problems of inconvenient discharge, product loss and contamination in existing reaction devices.

[0105] Correspondence analysis of the attached figures Figure 8 analyze: Figure 8 The design of the bottom discharge structure of the electrochemical cell 8 is shown, which intuitively demonstrates the technical features of gravity discharge and no residue. This strongly proves that the device of the present invention is convenient and pollution-free, and demonstrates the point that the device of the present invention is integrated and easy to operate.

[0106] 10. Examples (Technical solutions: two sets of specific process parameters, Example A and Example B) Compared to the shortcomings of existing technologies, such as the lack of standardized electrochemical modification processes, ambiguous parameters, and unrepeatable effects, this patent innovatively and non-obviously standardizes precise raw material ratios, device assembly processes, temperature and electrical synergy parameters, and post-treatment conditions to form a replicable modification process. Examples A and B are adapted to different scales and reaction time requirements, respectively. Strict parameter control ensures a significant reduction in interfacial tension and a substantial reduction in emulsion particle size, resulting in stable and repeatable modification effects. This provides a standardized solution for industrial production and solves the defects of existing technologies, such as the lack of standardized processes and uncontrollable product performance.

[0107] Correspondence analysis of the attached figures Figure 2 , Figure 4 analyze: Figure 2 The data show the stability of the physicochemical parameters of pectin, proving that the modified skeleton structure is intact; Figure 4 The particle size distribution diagrams of the emulsions in Examples 1 to 5 are shown. The average particle size decreased from 2.14 μm to 1.16 μm, which strongly proves that the standardized process of the present invention can stably achieve the refinement of emulsion particle size and the improvement of emulsification performance, and demonstrates the view that the process of the present invention is repeatable and has excellent performance.

[0108] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claims.

Claims

1. A pectin electrochemical modification and emulsification enhancement method for shortening the preparation cycle and synergistically regulating interfacial tension, characterized in that, The method includes the following steps: Step 1: Disperse pectin in the reaction medium and hydrate it, stirring until homogeneous to obtain a pectin solution; Step 2: Pour the pectin solution into the electrochemical reaction cell, turn on the magnetic stirrer and use the temperature control system to adjust and maintain the pectin solution at the set temperature; then turn on the power to start the anode and cathode working. The pectin structure is reshaped in a synergistic manner using electric and temperature fields: the charge density is enhanced by electrochemical polarization and redox effects, the molecular weight and conformational evolution are controlled by precise temperature control, and the conformational rearrangement of endogenous proteins is induced by electric field force, thereby synergistically enhancing its emulsifying performance and stability in the dimensions of electrostatic shielding, steric hindrance and interfacial rheology. After the reaction is complete, the modified material is removed; Step 3: The modified material is subjected to alcohol precipitation and drying to obtain structure-modified pectin.

2. The pectin electrochemical modification emulsification enhancement method for shortening the preparation cycle and synergistically regulating interfacial tension as described in claim 1, characterized in that, In step two: the pectin conformation is reshaped in a synergistic manner by electric and temperature fields, and endogenous protein conformational rearrangement is induced by electrochemical polarization to expose hydrophobic groups, thereby significantly enhancing emulsification performance from the perspectives of electrostatic shielding and interfacial rheology.

3. The pectin electrochemical modification emulsification enhancement method for shortening the preparation cycle and synergistically regulating interfacial tension as described in claim 1, characterized in that, The reaction medium is a 0.5-10% (v / v) aqueous solution of ethanol, and the dilution water is selected from at least one of distilled water, tap water or deionized water; The concentration of the pectin solution is 1-5% (w / w), and the dispersion and hydration time is 10-20 h; The temperature of the electrochemical cell was kept constant at 0–30 °C during the electrochemical modification process; The electrochemical modification voltage ranges from 10 to 1000 V, and the reaction time ranges from 10 to 60 min.

4. The pectin electrochemical modification emulsification enhancement method for shortening the preparation cycle and synergistically regulating interfacial tension as described in claim 1, characterized in that, In step three: add 3 times the volume of 75-100% (v / v) ethanol to the modified material, centrifuge at 5000-18000 rpm for 5-25 min; then dry at 40-75℃ to obtain the structure-modified pectin.

5. The pectin electrochemical modification emulsification enhancement method for shortening the preparation cycle and synergistically regulating interfacial tension as described in claim 1, characterized in that, In step two: the anode and cathode electrodes are platinum metal sheets, and the magnetic stirrer in the electrochemical reaction cell rotates at 100–500 rpm.

6. The pectin electrochemical modification emulsification enhancement method for shortening the preparation cycle and synergistically regulating interfacial tension as described in claim 1, characterized in that, By utilizing electrochemical polarization and redox effects, the charge density of molecules is effectively enhanced, significantly improving the electrostatic repulsion between droplets. At the same time, by precisely controlling the molecular weight and conformation through temperature control, the hydrophilic-hydrophobic balance is optimized, resulting in the modified pectin exhibiting a faster adsorption rate and lower interfacial tension at the oil-water interface.

7. By inducing conformational rearrangement of pectin endogenous proteins using an electric field, hydrophobic groups are fully exposed, thereby constructing a high-strength interfacial film. This synergistic enhancement from three dimensions—electrostatic shielding, steric hindrance, and interfacial rheology—enables the generated emulsion to exhibit superior stability in complex environments, effectively preventing droplet aggregation and separation.

8. A pectin electrochemical modification emulsification and enhancement device for shortening the preparation cycle and synergistically regulating interfacial tension, characterized in that, Used to implement the method according to claims 1-6, The electrochemical modification device is a dedicated electrochemical modification device; Its structure is as follows: The device includes an electrode holder (1), the electrode holder includes a top (2) and a bottom (4), and also includes a connecting rod (3). The top (2) and the bottom (4) are connected by evenly distributed connecting rods (3). The surface of the connecting rod (3) includes a set of symmetrical grooves for accommodating the protrusions (13) of the platinum sheet electrode (5). The bottom (4) of the holder is provided with a ring-shaped limiting groove for fixing the bottom end of the electrode. The platinum electrode (5) is symmetrically inserted into the electrode holder (1). The electrode is inserted, removed and expanded by the metal pull ring (6) at the top of the electrode. The electrode holder (1) is installed or removed by the holder handle (7). The electrode holder (1) with the platinum electrode (5) inserted is placed in the cylindrical double-layer water bath sealed electrochemical cell (8), with the electrode holder (1) closely attached to the inner wall of the electrochemical cell (8). The cylindrical double-layer water bath sealed electrochemical cell (8) is connected to the inlet (9) and the outlet (10). The space between the electrochemical cell (8) and the electrode holder (1) is the water bath space (11). The temperature of the pectin solution can be controlled by pumping in cooling circulating water into the water bath space. The magnetic stir bar (12) is placed in the cylindrical double-layer water bath sealed electrochemical cell (8) to make the temperature of the pectin solution uniformly distributed; The supporting device can achieve flexible insertion and removal of electrodes and expansion of the number of electrodes through a fixing frame with symmetrical cuboid grooves and metal pull rings; the electrochemical cell adopts a "bottom in, top out" double-layer sealed water bath structure, combined with magnetic stirring to ensure uniform field distribution, which can effectively avoid polysaccharide degradation caused by local overheating.

9. The pectin electrochemical modification emulsification and enhancement device for shortening the preparation cycle and synergistically regulating interfacial tension as described in claim 7, characterized in that, Before electrochemical modification begins, adjust the number of platinum sheet electrodes (5) on the electrode holder (1); After the electrochemical modification is completed, pull up the handle (7) of the fixing frame to facilitate the quick removal of the electrode fixing frame (1); then pull up the metal pull ring (6) to quickly disassemble the platinum electrode (5); the bottom of the electrochemical cell (8) contains an outlet, which contains a valve that can discharge the electrochemically modified liquid.

10. A pectin electrochemical modification and emulsification enhancement method for shortening the preparation cycle and synergistically regulating interfacial tension, characterized in that, The method is any one of the following: A. (1) Disperse 12g of orange peel pectin in 400g of distilled water containing 5% (v / v) ethanol, and stir at room temperature for 10h to fully hydrate the pectin and obtain a pectin solution with uniform concentration. (2) Insert the platinum sheet electrodes symmetrically into the electrode holder and connect them to the anode and cathode of the DC power supply respectively; connect the cooling circulating water device to the inlet and outlet of the 500mL cylindrical double-layer water bath sealed electrochemical cell, and then place the electrode holder with the electrodes installed into the electrochemical cell to complete the assembly of the modification device. (3) Take 300 mL of pectin solution prepared in step (1) and add it to the electrochemical modification device described in (2). Turn on the magnetic stirrer and adjust the speed to 300 rpm. Start the cooling water circulator and adjust the flow rate to 8L / min to adjust and maintain the temperature of the pectin solution at 10-15℃; (4) After the temperature of the pectin solution in step (3) stabilizes, turn on the DC power supply, adjust the voltage to 200V, and react with the electric field and temperature field for 30 minutes. (5) After the reaction is complete, take out the modified product described in step (4), add 3 times the volume of 95% (v / v) ethanol to it for alcohol precipitation, centrifuge the mixture at 5000-18000 rpm for 10 min, discard the supernatant and collect the precipitated pectin. (6) Finally, place the pectin from step (5) in an electric heating drying oven and dry it at 50°C to a constant weight to obtain the structure-modified and strengthened pectin. B. (1) Disperse 16g of orange peel pectin in 400g of distilled water containing 6% (v / v) ethanol, and stir at room temperature for 12h to fully hydrate the pectin and obtain a pectin solution with uniform concentration. (2) Insert two sets of platinum sheet electrodes (120mm×10mm in size) symmetrically into the electrode holder and connect them to the anode and cathode of the DC power supply respectively; connect the cooling circulating water device to the inlet and outlet of the 500mL cylindrical double-layer water bath sealed electrochemical cell, and then place the electrode holder with the electrodes installed into the electrochemical cell to complete the assembly of the modification device. (3) Take 400 mL of the pectin solution prepared in step (1) and add it to the electrochemical modification device described in (2). Turn on the magnetic stirrer and adjust the speed to 200-400 rpm. Start the cooling water circulator and adjust the flow rate to 12L / min to adjust and maintain the temperature of the pectin solution at 15-25℃; (4) After the temperature of the pectin solution in step (3) stabilizes, turn on the DC power supply, adjust the voltage to 300V, and react with the electric field and temperature field for 15min, 30min, 45min and 60min respectively. (5) After the reaction is complete, take out the modified product described in step (4), add 3 times the volume of 95% (v / v) ethanol to it for alcohol precipitation, centrifuge the mixture at 15000 rpm for 15 min, discard the supernatant and collect the precipitated pectin. (6) Finally, place the pectin from step (5) in an electric heating drying oven and dry it at 45°C to constant weight to obtain the structure-modified and strengthened pectin.

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