Method and device for separating synephrine and naringin in extract of fructus aurantii

Abstract

This invention discloses a method and apparatus for separating synephrine and naringin from Citrus aurantium extract, belonging to the field of traditional Chinese medicine separation technology. Based on ion-exchange membrane electrodialysis, this invention utilizes the special properties of ion-exchange membranes to achieve efficient separation of naringin and synephrine from Citrus aurantium extract. By adding acidic solutions such as hydrochloric acid, the alkaloids such as synephrine in the Citrus aurantium extract exist in ionic form, thereby directly separating synephrine and naringin through ion-exchange membrane electrodialysis. This invention can efficiently separate synephrine and naringin from Citrus aurantium extract, recovering over 90% of synephrine, greatly improving the efficiency and safety of synephrine recovery. Simultaneously, sodium chloride and hydrochloric acid can also be recovered, enhancing the economic efficiency of the process. Furthermore, this process consumes no chemical reagents and has low energy consumption, making it an economical, green, environmentally friendly, and highly efficient production method with significant industrial application value.

Description

Technical Field

[0001] The present invention belongs to the technical field of traditional Chinese medicine separation, and particularly relates to a method and device for separating synephrine and naringin from the extract of Fructus Aurantii Immaturus. Background Art

[0002] Fructus Aurantii Immaturus is the dried young fruit of Citrus aurantium L. and its cultivated varieties or sweet orange of Rutaceae family, which has the effects of promoting qi circulation to relieve accumulation, resolving phlegm and relieving stuffiness. Clinically, it is mainly used to treat gastrointestinal accumulation, damp-heat dysentery, chest impediment, knotted chest, qi stagnation and chest pain, postpartum abdominal pain and other diseases. The effective components of Fructus Aurantii Immaturus are complex, mainly including alkaloids, volatile oils and flavonoid compounds. Synephrine is an important alkaloid that plays a major role in Fructus Aurantii Immaturus, with the molecular formula of C9H 13 NO2, which has the effects of constricting blood vessels, raising blood pressure and dilating trachea. Clinically, it is used to treat septic shock, anaphylactic shock and other diseases. In addition, some studies have shown that synephrine can improve metabolism, increase calorie consumption and oxidize fat. It is a natural stimulant. Compared with ephedrine, it has no side effects and addiction. Therefore, synephrine is widely used in industries such as medicine, food and beverage.

[0003] The existing preparation process of synephrine generally includes two steps: extraction and separation and purification. Generally, acid water extraction is first used, and then cation exchange resin or macroporous adsorption resin and organic solvent extraction are used for separation and purification. Among them, both the extract of Fructus Aurantii Immaturus and the eluate obtained by resin contain a large amount of impurity components represented by flavonoids, which will seriously affect the color, stability and safety of the product. Moreover, the above process has problems such as large consumption of organic reagents, high energy consumption, complex process and low separation efficiency, and it is difficult to achieve green manufacturing of traditional Chinese medicine. Summary of the Invention

[0004] In view of the above problems, the present invention provides a method for separating synephrine and naringin from the extract of Fructus Aurantii Immaturus. The separation method is carried out by a separation device, and the separation device at least includes a group of electrodialysis units. The electrodialysis units are sequentially provided with cation exchange membranes, anion exchange membranes, cation exchange membranes and cation exchange membranes from the anode plate to the cathode plate direction. Salt recovery chambers, raw material chambers and product chambers are sequentially formed between adjacent exchange membranes; an anode chamber is formed between the cation exchange membrane close to the anode plate and the anode plate, and a cathode chamber is formed between the cation exchange membrane close to the cathode plate and the cathode plate;

[0005] The separation method includes the following steps:

[0006] Adding a salt solution to the storage tanks corresponding to the salt recovery chamber and the product chamber;

[0007] Adding an electrolyte solution to the storage tanks corresponding to the anode chamber and the cathode chamber;

[0008] Add the extract of Citrus aurantium containing synephrine and naringin to the storage tank corresponding to the raw material chamber;

[0009] A constant voltage is applied between the anode plate and the cathode plate to separate the extract of Citrus aurantium in a constant voltage operating mode until the current density drops to a set value and the separation stops.

[0010] Furthermore, the salt solution is a sodium chloride solution with a concentration of 0-0.2 mol / L.

[0011] Furthermore, the electrolyte solution is a sodium sulfate solution with a concentration of 0.01-0.4 mol / L.

[0012] Furthermore, the concentration of synephedrine in the Fructus Aurantii Immaturus extract is 0.01-0.1 mol / L, and the concentration of naringin is 0.01-0.1 mmol / L.

[0013] Furthermore, the membrane pair voltage of each electrodialysis unit does not exceed 25V.

[0014] Furthermore, the separation device operates until the current density drops to ≤3mA / cm². 2 Separation will stop at this time.

[0015] On the other hand, the present invention proposes a separation device for synephrine and naringin in the extract of Citrus aurantium, the separation device comprising: an anode plate, a cathode plate and a membrane stack disposed between the anode plate and the cathode plate;

[0016] The membrane stack forms an anode chamber and a cathode chamber between its two sides and the anode plate and the cathode plate, respectively; the membrane stack includes at least one set of electrodialysis units, and each set of electrodialysis units is arranged in the order of one cation exchange membrane, one anion exchange membrane, one cation exchange membrane, and one cation exchange membrane from the anode plate to the cathode plate to form three compartments;

[0017] A salt recovery chamber is formed between the cation exchange membrane and the anion exchange membrane, a raw material chamber is formed between the anion exchange membrane and the cation exchange membrane, and a product chamber is formed between the cation exchange membranes; a storage tank and a circulation pump are provided in the anode chamber, cathode chamber, recovery chamber, raw material chamber, and product chamber.

[0018] The storage tanks corresponding to the salt recovery chamber and the product chamber are used to add salt solution;

[0019] The storage tanks corresponding to the anode chamber and cathode chamber are used to add electrolyte solution;

[0020] The storage tank corresponding to the raw material chamber is used to add the extract of Citrus aurantium containing synephrine and naringin.

[0021] Furthermore, the anode chamber, cathode chamber, salt recovery chamber, raw material chamber, and product chamber are each equipped with an inlet and an outlet, and are connected to their respective storage tanks via pipelines, forming a self-circulating loop powered by their respective circulating pumps.

[0022] The beneficial effects of this invention are:

[0023] This invention is based on ion-exchange membrane electrodialysis, utilizing the unique properties of ion-exchange membranes to achieve efficient separation of naringin and synephrine in the extract of Citrus aurantium. By adding acidic solutions such as hydrochloric acid, the alkaloids such as synephrine in the Citrus aurantium extract are kept in ionic form, allowing for direct separation of synephrine and naringin via ion-exchange membrane electrodialysis. This method avoids the shortcomings of existing processes in separating synephrine, such as low efficiency, high energy consumption, and significant environmental pollution. The separation device efficiently separates synephrine and naringin from the Citrus aurantium extract, recovering over 90% of synephrine, greatly improving the efficiency and safety of synephrine recovery. Simultaneously, sodium chloride and hydrochloric acid are also recovered, enhancing the economic efficiency of the process. Furthermore, this process consumes no chemical reagents and has low energy consumption, making it an economical, green, environmentally friendly, and highly efficient production method with significant industrial application value.

[0024] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained by means of the structures pointed out in the description, claims and drawings. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 A schematic diagram illustrating the principle of electrodialysis separation of synephrine and naringin proposed in an embodiment of the present invention is shown;

[0027] Figure 2 The flowchart of the method for separating synephrine and naringin from the extract of Citrus aurantium proposed in this invention is shown. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] like Figure 1 As shown, the separation device for synephedrine and naringin in the extract of Citrus aurantium of the present invention includes: an anode plate, a cathode plate, and a membrane stack disposed between the anode plate and the cathode plate;

[0030] The cation exchange membrane in the diagram is the cation exchange membrane, and the anion exchange membrane is the anion exchange membrane. The ion exchange membranes used in the membrane stack are CIS cation exchange membranes and AIS anion exchange membranes manufactured by Shandong Tianwei Membrane Technology Co., Ltd., with an effective area of ​​20 cm² per membrane. 2 + indicates anode, - indicates cathode, C9H 13 NO2H + For Sinfeld, C 27 H 32 O 14 It is naringin.

[0031] The membrane stack forms an anode chamber and a cathode chamber on its two sides, respectively, with respect to the anode plate and the cathode plate. The membrane stack includes at least one set of electrodialysis units, the number of which can be 2-1000. Each set of electrodialysis units is arranged in three compartments in the order of one cation exchange membrane, one anion exchange membrane, one cation exchange membrane, and one cation exchange membrane from the anode plate to the cathode plate.

[0032] The compartment between the cation exchange membrane and the anion exchange membrane is a salt recovery compartment, the compartment between the anion exchange membrane and the cation exchange membrane is a raw material compartment, and the compartment between the cation exchange membranes is a product compartment. Each of the anode compartment, cathode compartment, recovery compartment, raw material compartment, and product compartment is equipped with a storage tank and a circulation pump. Each compartment is connected to the corresponding storage tank through pipelines and forms a self-circulating loop powered by its respective circulation pump.

[0033] like Figure 2 As shown, the method for separating synephrine and naringin from the extract of Citrus aurantium proposed in this invention includes the following steps:

[0034] Add salt solution to the storage tanks corresponding to the salt recovery chamber and the product chamber;

[0035] Add electrolyte solution to the storage tanks corresponding to the anode and cathode chambers;

[0036] Add the Citrus aurantium extract containing synephrine and naringin to the storage tank corresponding to the raw material chamber; the pH of the Citrus aurantium extract is adjusted to acidic using hydrochloric acid, and the concentration and amount of hydrochloric acid are not specifically limited in this invention;

[0037] A constant voltage operating mode is used to separate the extract of Citrus aurantium by applying a direct current between the anode and cathode plates until the current density drops to a set value, at which point the separation stops. During the separation process, the anode chamber, cathode chamber, recovery chamber, raw material chamber, and product chamber are self-circulating. The salt recovery chamber can recover sodium chloride and hydrochloric acid.

[0038] Because too low a concentration of salt solution and sodium chloride solution would result in a high initial voltage of the membrane stack and high energy consumption, while too high a concentration would lead to intensified ion back diffusion and affect mass transfer in the separation process, the salt solution selected in this invention is a sodium chloride solution with a concentration of 0-0.2 mol / L, and the electrolyte selected is a sodium sulfate solution with a concentration of 0.01-0.4 mol / L.

[0039] Example 1

[0040] This embodiment uses, as follows: Figure 1 The separation device shown has the following membrane stack arrangement: anode - anode chamber - cation exchange membrane - [salt recovery chamber - anion exchange membrane - feed chamber - cation exchange membrane - product chamber - cation exchange membrane]. n -Cathode Chamber-Cathode, with 2 repeating units. The anode and cathode materials are corrosion-resistant titanium coated with ruthenium. The anode chamber, cathode chamber, recovery chamber, raw material chamber, and product chamber are all equipped with inlets and outlets. Each chamber is connected to the corresponding storage tank through pipelines and forms a self-circulating loop powered by its own circulation pump.

[0041] The anode and cathode plates form an anode chamber and a cathode chamber respectively with the adjacent membranes. These chambers are connected in series and 200 mL of 0.3 mol / L sodium sulfate is introduced as the electrode solution. The salt recovery chamber is introduced with 200 mL of 0.1 mol / L sodium chloride solution. The feed chamber is introduced with 200 mL of a mixed solution of 0.01 mol / L synephrine and 0.086 mmol / L naringin (pH 4). The product chamber is introduced with 200 mL of 0.2 mol / L sodium chloride solution. During the experiment, the linear velocity of the solution flow in each chamber was 3 cm / s, and a constant voltage operation mode was used, with the membrane stack voltage set to 20 V.

[0042] During the separation process, the voltage (i.e., membrane-to-cell voltage) of each electrodialysis unit remained stable at 8.7–8.9 V, and the separation device operated until the current density reached 1 mA / cm². 2 The process ended. Ultimately, the recovery rate of synephrine in the product chamber was 57.6%, and naringin was not detected in the product chamber. The energy consumption was 2.0 kWh / kg.

[0043] Example 2

[0044] The separation device used in this embodiment is the same as that in Embodiment 1.

[0045] The anode and cathode plates form an anode chamber and a cathode chamber with the adjacent membrane. These chambers are connected in series and 200 mL of 0.4 mol / L sodium sulfate is introduced as the electrode solution. The salt recovery chamber is introduced with 200 mL of 0.1 mol / L sodium chloride solution. The feed chamber is introduced with 200 mL of a mixed solution of 0.01 mol / L synephrine and 0.086 mmol / L naringin (pH 4). The product chamber is introduced with 200 mL of 0.2 mol / L sodium chloride solution. During the experiment, the linear velocity of the solution flow in each chamber was 3 cm / s, and a constant voltage operation mode was used, with the membrane stack voltage set to 30 V.

[0046] During the separation process, the voltage of each electrodialysis unit remained stable at 13.6–13.9 V, and the separation device operated until the current density reached 1 mA / cm². 2 The process ended. Ultimately, the recovery rate of synephrine in the product chamber was 66.8%, and no naringin was detected in the product chamber. The energy consumption was 3.6 kWh / kg.

[0047] Example 3

[0048] The separation device used in this embodiment is the same as that in Embodiment 1.

[0049] The anode and cathode plates form an anode chamber and a cathode chamber with the adjacent membranes, respectively. These chambers are connected in series and 200 mL of 0.4 mol / L sodium sulfate is introduced as the electrode solution. The salt recovery chamber is introduced with 200 mL of 0.1 mol / L sodium chloride solution. The feed chamber is introduced with 200 mL of a mixed solution of 0.01 mol / L synephrine and 0.086 mmol / L naringin (pH 4). The product chamber is introduced with 200 mL of 0.2 mol / L sodium chloride solution. During the experiment, the linear velocity of the solution flow in each chamber was 3 cm / s, and a constant voltage operation mode was used, with the membrane stack voltage set to 40 V.

[0050] During the separation process, the voltage of each electrodialysis unit remained stable at 18.5–18.9 V, and the separation device operated until the current density reached 1.5 mA / cm². 2 The process ended at that time. Ultimately, the recovery rate of synephrine in the product chamber was 88.9%, and no naringin was detected in the product chamber. The energy consumption was 5.8 kWh / kg.

[0051] Example 4

[0052] The separation device used in this embodiment is the same as that in Embodiment 1.

[0053] The anode and cathode plates form an anode chamber and a cathode chamber with the adjacent membranes, respectively. These chambers are connected in series and 200 mL of 0.4 mol / L sodium sulfate is introduced as the electrode solution. The salt recovery chamber is introduced with 200 mL of 0.1 mol / L sodium chloride solution. The feed chamber is introduced with 200 mL of a mixed solution of 0.01 mol / L synephrine and 0.086 mmol / L naringin (pH 4). The product chamber is introduced with 200 mL of 0.2 mol / L sodium chloride solution. During the experiment, the linear velocity of the solution flow in each chamber was 3 cm / s, and a constant voltage operation mode was used, with the membrane stack voltage set to 50 V.

[0054] During the separation process, the voltage of each electrodialysis unit remained stable at 23.4–23.9 V, and the separation device operated until the current density reached 1.5 mA / cm². 2 The process ended. Ultimately, the recovery rate of synephrine in the product chamber was 94.4%, and no naringin was detected in the product chamber. The energy consumption was 10.1 kWh / kg.

[0055] Example 5

[0056] The separation device used in this embodiment is the same as that in Embodiment 1.

[0057] The anode and cathode plates form an anode chamber and a cathode chamber with the adjacent membrane. These chambers are connected in series and 200 mL of 0.4 mol / L sodium sulfate is introduced as the electrode solution. The salt recovery chamber is introduced with 200 mL of 0.1 mol / L sodium chloride solution. The feed chamber is introduced with 200 mL of a mixed solution of 0.02 mol / L synephrine and 0.086 mmol / L naringin (pH 4). The product chamber is introduced with 200 mL of 0.2 mol / L sodium chloride solution. During the experiment, the linear velocity of the solution flow in each chamber was 3 cm / s, and a constant voltage operation mode was used, with the membrane stack voltage set to 40 V.

[0058] During the separation process, the voltage of each electrodialysis unit remained stable at 18.4–18.9 V, and the separation device operated until the current density reached 1 mA / cm². 2 The process ended. Ultimately, the recovery rate of synephrine in the product chamber was 95.8%, and no naringin was detected in the product chamber. The energy consumption was 5.1 kWh / kg.

[0059] Example 6

[0060] The separation device used in this embodiment is the same as that in Embodiment 1.

[0061] The anode and cathode plates form an anode chamber and a cathode chamber with the adjacent membranes, respectively. These chambers are connected in series and 200 mL of 0.4 mol / L sodium sulfate is introduced as the electrode solution. The salt recovery chamber is introduced with 200 mL of 0.1 mol / L sodium chloride solution. The feed chamber is introduced with 200 mL of a mixed solution of 0.04 mol / L synephrine and 0.086 mmol / L naringin (pH 4). The product chamber is introduced with 200 mL of 0.2 mol / L sodium chloride solution. During the experiment, the linear velocity of the solution flow in each chamber was 3 cm / s, and a constant voltage operation mode was used, with the membrane stack voltage set to 40 V.

[0062] During the separation process, the voltage of each electrodialysis unit remained stable at 18.3–18.9 V, and the separation device operated until the current density reached 0.5 mA / cm². 2 The process ended. Ultimately, the recovery rate of synephrine in the product chamber was 97.5%, and no naringin was detected in the product chamber. The energy consumption was 5.5 kWh / kg.

[0063] The experimental conditions, synephrine recovery rate, and energy consumption in Examples 1-6 are shown in Table 1:

[0064] Table 1. Experimental conditions and results in Examples 1-6

[0065]

[0066] As can be seen from the above embodiments, the separation method proposed in this invention can effectively separate synephrine and naringin. Furthermore, it can be seen that, at different synephrine concentrations, stabilizing the membrane voltage below 25V and controlling the termination current density to ≤1mA / cm² is effective. 2 At this point, the recovery rate of synephrine can reach over 95%. Although it can be seen from Examples 3 and 4 that the recovery rate of synephrine is higher at higher membrane pair voltages, the energy consumption increases significantly. Therefore, the membrane pair voltage should not be too high, and a membrane pair voltage of 18-19V is preferred. When the concentration of synephrine is 0.04mol / L, due to the increase in solution concentration and the decrease in solution resistance, the separation device runs for a longer time, the separation is more thorough, and the maximum recovery rate of synephrine can reach 97.5%.

[0067] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for separating synephrine and naringin from Citrus aurantium extract, characterized in that, The separation method is carried out by a separation device, which includes at least one set of electrodialysis units. The electrodialysis units are arranged sequentially from the anode plate to the cathode plate with cation exchange membranes, anion exchange membranes, cation exchange membranes, and cation exchange membranes. A salt recovery chamber, a raw material chamber, and a product chamber are formed sequentially between adjacent exchange membranes. An anode chamber is formed between the cation exchange membrane near the anode plate and the anode plate, and a cathode chamber is formed between the cation exchange membrane near the cathode plate and the cathode plate. The separation method includes the following steps: A salt solution is added to the storage tanks corresponding to the salt recovery chamber and the product chamber; the salt solution is a sodium chloride solution with a concentration of 0-0.2 mol / L. An electrolyte solution is added to the storage tanks corresponding to the anode and cathode chambers; the electrolyte solution is a sodium sulfate solution with a concentration of 0.01-0.4 mol / L. Add the extract of Citrus aurantium containing synephrine and naringin to the storage tank corresponding to the raw material chamber; the concentration of synephrine in the Citrus aurantium extract is 0.01-0.1 mol / L and the concentration of naringin is 0.01-0.1 mmol / L. A constant voltage is applied between the anode and cathode plates to separate the extract of Citrus aurantium in a constant voltage operating mode until the current density drops to a set value, at which point separation stops. The membrane pair voltage of each electrodialysis unit is 18.3-18.9V. The separation device operates until the current density drops to ≤3 mA / cm². 2 Separation will stop at this time.

2. A device for separating synephrine and naringin from Citrus aurantium extract, characterized in that, The separation device includes: an anode plate, a cathode plate, and a membrane stack disposed between the anode plate and the cathode plate; The membrane stack forms an anode chamber and a cathode chamber on its two sides, respectively, with respect to the anode plate and cathode plate. The membrane stack includes at least one set of electrodialysis units, each set consisting of three compartments arranged sequentially from the anode plate to the cathode plate, with one cation exchange membrane, one anion exchange membrane, one cation exchange membrane, and one cation exchange membrane. The membrane pair voltage of each set of electrodialysis units is 18.3-18.9V. The separation device operates until the current density drops to ≤3 mA / cm². 2 Separation stops at this time; A salt recovery chamber is formed between the cation exchange membrane and the anion exchange membrane, a raw material chamber is formed between the anion exchange membrane and the cation exchange membrane, and a product chamber is formed between the cation exchange membranes; a storage tank and a circulation pump are provided in the anode chamber, cathode chamber, recovery chamber, raw material chamber, and product chamber. The storage tanks corresponding to the salt recovery chamber and product chamber are used to add salt solution; the salt solution is a sodium chloride solution with a concentration of 0-0.2 mol / L; the electrolyte solution is a sodium sulfate solution with a concentration of 0.01-0.4 mol / L. The storage tanks corresponding to the anode and cathode chambers are used to add electrolyte solution; the electrolyte solution is a sodium sulfate solution with a concentration of 0.01-0.4 mol / L. The storage tank corresponding to the raw material chamber is used to add a bitter orange extract containing synephrine and naringin; the concentration of synephrine in the bitter orange extract is 0.01-0.1 mol / L and the concentration of naringin is 0.01-0.1 mmol / L.

3. The device for separating synephrine and naringin from the extract of Citrus aurantium according to claim 2, characterized in that, The anode chamber, cathode chamber, salt recovery chamber, raw material chamber, and product chamber are all equipped with inlets and outlets, and are connected to their respective storage tanks through pipelines, forming a self-circulating loop powered by their respective circulation pumps.

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