Solid-liquid adsorption / hot gas desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid

Abstract

The invention belongs to the technical field of forest chemical industry and natural perfume extraction and separation, and particularly discloses a solid-liquid adsorption / hot gas desorption separation and recovery method for perfume components in cinnamon oil extraction waste liquid. According to the method, macroporous resin and the like are used as solid-phase adsorbents to adsorb and enrich spice components such as coumarin, cinnamic acid, cinnamyl aldehyde and the like in the waste liquid, then hot inert gas or water vapor is used as a gas-phase desorption medium to perform thermal desorption on the solid-phase adsorbents adsorbing and enriching the spice components, and the separated mixed gas is subjected to condensation cooling and phase separation to obtain the coumarin-cinnamic acid-cinnamyl aldehyde. And collecting to obtain crystalline solids such as cinnamon aromatic water, cinnamon oil or coumarin and the like. The method provided by the invention can effectively separate and recover spice components in the cinnamon oil extraction waste liquid, and has the advantages of low equipment investment, simple and feasible operation, low production cost, clean and pollution-free process, good operation safety, high industrial application feasibility and the like.

Description

Technical Field

[0001] This invention belongs to the field of forest chemical industry and natural fragrance extraction and separation technology. Specifically, it relates to a method for recycling and treating waste or residues from cinnamon oil extraction, and more specifically, a solid-liquid adsorption / thermal desorption separation and recovery method for fragrance components in cinnamon oil extraction waste liquid. Background Technology

[0002] Cinnamon oil, an aromatic oil obtained by distillation from the bark, branches, and leaves of the cinnamon tree (Cinnamomum cassia Presl), a plant in the Lauraceae family, has the effects of dispelling wind and dampness, and warming and strengthening the spleen and stomach. Cinnamon oil contains active ingredients such as cinnamaldehyde and cinnamic acid, which have antibacterial, anti-inflammatory, and blood circulation-promoting effects. It is commonly used for rheumatism, itchy skin, spleen and stomach deficiency, cold limbs and weak pulse, cold accumulation in the epigastrium and abdomen, abdominal pain and diarrhea, and cold hernia. Cinnamon oil can be used in feed, food, spices, and external medicines. Cinnamon oil extraction waste liquid refers to the aqueous phase residue discharged from the re-distillation pot or distillation pot that also serves as a re-distillation vessel during the steam distillation process of cinnamon oil extraction. Cinnamon oil extraction wastewater contains dissolved or dispersed natural cinnamon flavoring components such as coumarins, cinnamic acid, cinnamaldehyde, and o-methoxycinnamaldehyde. Although the concentration of these flavoring components is low, the large volume and high temperature of the wastewater (reaching 100°C when discharged from the pot) mean that direct discharge would not only waste a significant amount of natural flavoring but also cause ecological imbalance in the aquatic environment. Therefore, the resource utilization and treatment of this wastewater, especially the separation and recovery of its flavoring components, has significant economic and social implications. Currently, there are few research reports on the resource utilization of cinnamon oil extraction wastewater in domestic and international literature. The main method for separating and recovering cinnamon flavoring components is solvent extraction (see references 1-3 attached). However, this method uses organic solvents such as dichloromethane and ethyl acetate as extractants, which poses risks of operational safety, solvent residue, and environmental pollution, making it difficult to widely promote and apply in enterprises.

[0003] References: [1] RANASINGHE L, JAYAWARDENA B, ABEYWICKRAMA K, et al. Use of wastegenerated from cinnamon bark oil (CinnamomumzeylanicumBlume) extraction as apost-harvest treatment for Embul banana[J]. Journal of Food, Agriculture and Environment, 2003, 1 (2): 340-344.

[0004] [2] Tian Yuhong. A method for preparing food preservatives using residue from cinnamon oil extraction reactor [P]. CN:201510439512.2, 2015-07-23.

[0005] [3] Tian Yuhong. Method for preparing mosquito repellent using residue from cinnamon oil extraction vessel [P]. CN:201510442543.3, 2015-07-23. Summary of the Invention

[0006] To address the problems existing in current methods for separating and recovering spice components from cinnamon oil extraction wastewater, this invention systematically studies the adsorption, separation, and desorption performance of solid-phase adsorbents such as macroporous resins on spice components in wastewater. It was found that solid-phase adsorbents such as macroporous resins have good adsorption and enrichment effects on spice components in wastewater. The content of cinnamon spice components adsorbed and enriched by some solid-phase adsorbents is higher than that of cinnamon branches and leaves, and these components can be desorbed and released by heating with steam or thermal inert gas. Based on this, this invention proposes a solid-liquid adsorption / thermal desorption separation and recovery method for spice components in cinnamon oil extraction wastewater. This method uses macroporous resins as solid-phase adsorbents to adsorb and enrich low concentrations of cinnamon flavoring components such as coumarin and cinnamaldehyde in waste liquid. Then, hot inert gas or water vapor is used as the gas-phase desorption medium to perform hot gas desorption on the solid-phase adsorbent containing the flavoring components, causing the water and flavoring components to vaporize and desorb. The desorbed mixed gas is condensed, cooled, and phase-separated to collect cinnamon aromatic water, cinnamon oil, or crystalline solids such as coumarin. The operation is simple and easy to implement, and the process is clean and pollution-free.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: A solid-liquid adsorption / thermal desorption method for separating and recovering spice components from cinnamon oil extraction waste liquid includes the following steps: (1) Solid-liquid adsorption: At an adsorption operating temperature of room temperature to 100°C, the solid adsorbent is brought into full contact with the cinnamon oil extraction waste liquid to adsorb and enrich the cinnamon flavor components such as coumarin and cinnamaldehyde in the waste liquid. The adsorption time is 0.5 to 2 hours. When the adsorption reaches saturation or after the adsorption is completed, the solid adsorbent is separated from the waste liquid. The remaining liquid phase is analyzed and tested and then re-adsorbed, recycled or discharged. (2) Hot gas desorption: Hot gas at a certain pressure and flow rate is used as the desorption medium. It is introduced into a jacketed heat-insulated desorption device containing a solid adsorbent that has adsorbed fragrance components for hot gas desorption, so that water and fragrance components are vaporized and released. The released mixed gas is condensed and cooled, and phase separation is performed to collect cinnamon aromatic water, cinnamon oil or coumarin and other crystalline solids. The hot gas refers to water vapor or hot inert gas. The hot gas pressure is less than 0.2 MPa, the temperature is 80 to 180°C, and the desorption time is 0.5 to 6 h.

[0008] Furthermore, in the above-mentioned solid-liquid adsorption / thermal desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid, the cinnamon oil extraction waste liquid refers to the aqueous phase residue discharged from the re-distillation pot or distillation pot that also serves as a re-distillation pot during the steam distillation process of cinnamon oil extraction. The devices used for adsorption and desorption can be used independently or shared, and the operation mode can be intermittent or continuous. The phase separation operation includes gas-liquid, gas-solid, or oil-water phase separation.

[0009] Furthermore, the solid-phase adsorbent is a solid-phase adsorbent material comprising macroporous resin, wherein the macroporous resin includes HZ-826, HZ-835, HZ-16, AB-8, and XAD-4 type macroporous resins.

[0010] Furthermore, the inert gas includes nitrogen and carbon dioxide at room temperature and pressure, preferably nitrogen, which can be appropriately heated by a heater to become a hot inert gas. The water vapor comes from a water vapor generator and includes saturated water vapor at room pressure and superheated water vapor at room pressure.

[0011] Furthermore, in the above-mentioned solid-liquid adsorption / thermal desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid, the thermal desorption is divided into two desorption processes, namely thermal inert gas desorption and steam desorption, depending on the type of thermal medium. The specific operation steps are as follows: a. Thermal inert gas desorption: A certain flow rate of inert gas is heated to 80-100°C by a heater and then introduced into a jacketed desorption device containing a solid-phase adsorbent that has adsorbed fragrance components. This causes most of the moisture in the solid-phase adsorbent to vaporize and desorb, being carried away by the inert gas. The desorbed mixture is condensed, cooled, and the moisture is collected through phase separation. The inert gas is then appropriately pressurized and accelerated by a pump, reheated by a heater, and reintroduced into the desorption device for thermal desorption, thus achieving the recycling and reuse of the inert gas. When the collected moisture no longer increases significantly... For extended periods, the inert gas temperature is raised to 100–180°C using a heater, causing the fragrance components and residual moisture to vaporize and desorb, and be carried out with the inert gas. The desorbed mixed gas is then condensed, cooled, and phase-separated to collect crystalline solids such as cinnamon aromatic water, cinnamon oil, or coumarin. The cinnamon aromatic water is stored together and sold directly for application. Alternatively, it can be further separated and recovered as cinnamon oil through solid-liquid adsorption / thermal gas desorption. The inert gas is appropriately pressurized and accelerated by a gas pump, and then heated by a heater before being reintroduced into the desorption device until desorption is complete.

[0012] b. Steam desorption process: Steam at a certain pressure, temperature and flow rate is introduced into a jacketed desorption device containing a solid adsorbent that has adsorbed fragrance components. The water and fragrance components adsorbed in the solid adsorbent are vaporized and desorbed and carried out by the steam. The desorbed mixed gas is condensed and cooled to obtain cinnamon aromatic water, or it is introduced into the steam distillation process pipeline for cinnamon oil extraction and mixed with the distilled oil-water mixture. After condensation and cooling and oil-water separation, cinnamon oil and cinnamon aromatic water are collected, thereby realizing the separation and recovery of fragrance components in waste liquid.

[0013] Compared with existing methods for separating and recovering spice components from cinnamon oil extraction waste liquid, the method of the present invention has the following advantages: This invention provides a solid-liquid adsorption / thermal desorption separation and recovery method for fragrance components in cinnamon oil extraction waste liquid. It uses steam or hot inert gas as the gas-phase desorption medium, without using organic solvents, supercritical fluid CO2, or subcritical fluid butane as the desorption medium. This method has advantages such as low equipment investment, simple and easy operation, low production cost, clean and pollution-free process, good operational safety, and high feasibility for industrial application. Using this method, cinnamon oil extraction waste liquid can be effectively treated for resource utilization, separating and recovering cinnamon aromatic water, cinnamon oil, or coumarins and other crystalline solids, which has significant economic and social implications.

[0014] The present invention describes a solid-liquid adsorption / thermal desorption process for determining the chemical composition or changes in cinnamon oil extraction waste liquid, cinnamon aromatic water, cinnamon oil, and crystalline solid products such as coumarin using gas chromatography-mass spectrometry (GC-MS), ultraviolet (UV) absorption spectroscopy, or high-performance liquid chromatography (HPLC). For cinnamon oil extraction waste liquid and cinnamon aromatic water, a small sample is taken, appropriately diluted with distilled water, and directly analyzed by UV absorption spectroscopy or HPLC. For cinnamon oil and crystalline solid products, a small sample is taken, dissolved in anhydrous ethanol, and two drops of phenolphthalein indicator are added, followed by the addition of 25% tetramethylammonium hydroxide solution until the purple-red color persists for 30 seconds. The sample is then directly injected for GC-MS analysis.

[0015] Quantitative analysis of the samples was performed on a GC-2014C gas chromatograph, and the relative percentage content of each component was calculated using the peak area normalization method. Chromatographic conditions: DB-5 quartz capillary column (30 m × 0.25 mm × 0.25 μm), N2 as carrier gas, FID detector, injector temperature 250℃, detector temperature 250℃, injection volume 1 μL; temperature program: initial temperature 70℃ held for 2 min, first increased to 100℃ at 2℃ / min, then increased to 180℃ at 8℃ / min, and then increased to 240℃ at 2℃ / min.

[0016] Qualitative analysis of the samples was performed on a gas chromatograph-mass spectrometer (GC-MS) of model 8890-5977B. Identification of each volatile component was achieved by comparison with standards, searching the NIST20.L mass spectrometer library, and consulting literature. The chromatographic conditions were the same as those for the aforementioned quantitative GC-MS. The mass spectrometry conditions were: Agilent HP-5ms capillary column (30 m × 0.25 mm × 0.25 μm), He as carrier gas, vaporization chamber temperature 240℃, mass spectrometer interface temperature 250℃, EI ion source, EI ionization voltage 70 eV, ion source temperature 230℃, quadrupole temperature 150℃, and injection volume 1 μL. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the process flow for the solid-liquid adsorption / thermal desorption separation and recovery method of spice components in cinnamon oil extraction waste liquid according to the present invention. Figure 2 This is the ultraviolet absorption spectrum of the cinnamon oil extraction waste liquid during the adsorption process of HZ-826 macroporous resin in Example 1 of the present invention; Figure 3 This is the ultraviolet absorption spectrum of the cinnamon oil extraction waste liquid during the adsorption process of AB-8 type macroporous resin in Example 2 of the present invention; Figure 4 This is a gas chromatogram of coumarin solid obtained by hot nitrogen desorption of AB-8 type macroporous resin in Example 2 of the present invention. In the figure, (1) trans-cinnamonaldehyde; (2) cinnamic acid (calculated as methylated derivative); (3) coumarin; (4) 10-methylundecanoic acid (calculated as methylated derivative); (5) 2-methoxycinnamonaldehyde. Figure 5 This is the ultraviolet absorption spectrum of the desorbate during the superheated steam desorption process of HZ-16 macroporous resin in Example 5 of the present invention. Figure 6 This is the ultraviolet absorption spectrum of the desorbate during the superheated steam desorption process of HZ-16 macroporous resin in Example 6 of the present invention. Detailed Implementation

[0018] The present invention will be further described in detail below with reference to embodiments and accompanying drawings. The following description is merely for illustrative purposes and does not limit the scope of the invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the materials and reagents used in the following embodiments are commercially available unless otherwise specified. In the following embodiments, the cinnamon oil extraction waste liquid refers to the aqueous phase residue discharged from the re-distillation pot or a distillation pot that also serves as a re-distillation pot during the steam distillation process of cinnamon oil extraction; the devices used for adsorption and desorption can be used independently or jointly, and the operation mode can be intermittent or continuous. Example 1

[0019] A solid-liquid adsorption / thermal nitrogen desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid includes the following steps: (1) At an adsorption temperature of 45℃, HZ-826 macroporous resin was brought into full contact with cinnamon oil extraction waste liquid for 1 hour to adsorb and enrich cinnamon flavoring components such as coumarin and cinnamaldehyde in the waste liquid. When saturation adsorption was reached or after adsorption was completed, the solid phase and liquid phase were stopped from contacting each other, and the free water of HZ-826 macroporous resin was removed. The remaining liquid phase was analyzed and tested before being re-adsorbed, recycled, or discharged. The ultraviolet absorption spectrum of cinnamon oil extraction waste liquid during the adsorption process of HZ-826 macroporous resin is attached. Figure 2 .

[0020] (2) Nitrogen gas at atmospheric pressure (0.1 MPa) and a flow rate of 7.5 L / min is heated to 100°C by a heater and then introduced into a jacketed desorption device containing 44 g of HZ-826 macroporous resin saturated with fragrance components for thermal desorption. This causes most of the moisture to vaporize and desorb, and be carried away by the nitrogen gas. The desorbed mixture is condensed, cooled, and separated into gas and liquid phases to remove moisture. The nitrogen gas is then appropriately pressurized and accelerated by a gas pump, heated again by a heater, and reintroduced into the desorption device for thermal desorption. The process involves the recycling of nitrogen gas. When the collected moisture no longer increases significantly, the nitrogen temperature is raised to 180°C via a heater, causing the fragrance components and residual moisture to vaporize and desorb, being carried away with the nitrogen. The desorbed mixture is then condensed and cooled, undergoing gas-liquid-solid separation. The desorption time is 5 hours, yielding 1.6 mL of cinnamon aromatic water and 0.1 g of colorless crystalline solid. The nitrogen gas is then appropriately pressurized and accelerated via a gas pump, heated to 180°C by a heater, and reintroduced into the desorption device until desorption is complete. Gas chromatography-mass spectrometry analysis shows that the main component of the crystalline solid product is coumarin, with a relative content (GC peak area normalization method) of 80.63%. Example 2

[0021] A solid-liquid adsorption / thermal nitrogen desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid includes the following steps: (1) At an adsorption temperature of 45℃, the cinnamon oil extraction waste liquid was brought into full contact with AB-8 macroporous resin for 1 hour to adsorb and enrich cinnamon flavoring components such as coumarin and cinnamaldehyde in the waste liquid. When saturation adsorption was reached or after adsorption was completed, the solid phase and liquid phase were stopped from contacting each other, and the free water of AB-8 macroporous resin was removed. The remaining liquid phase was analyzed and tested before being re-adsorbed, recycled, or discharged. The ultraviolet absorption spectrum of the cinnamon oil extraction waste liquid during the adsorption process of AB-8 macroporous resin is shown in the attached figure. Figure 3 .

[0022] (2) Nitrogen gas at atmospheric pressure (0.1 MPa) and a flow rate of 7.5 L / min is heated to 80°C by a heater and then introduced into a jacketed desorption device containing 44 g of AB-8 type macroporous resin saturated with fragrance components for thermal desorption. This causes most of the moisture to vaporize and desorb, and be carried away by the nitrogen gas. The desorbed mixed gas is condensed, cooled, and separated into gas and liquid phases to remove moisture. The nitrogen gas is then appropriately pressurized and accelerated by a gas pump, heated again by a heater, and reintroduced into the desorption device for thermal desorption. The nitrogen gas is recycled and reused. When the collected moisture no longer increases significantly, the nitrogen temperature is raised to 140℃ using a heater, causing the fragrance components and residual moisture to vaporize and desorb, and be carried out with the nitrogen. The desorbed mixture is condensed and cooled, and then subjected to gas-liquid-solid separation. The desorption time is 4 hours, yielding 2.1 mL of cinnamon aromatic water and 0.15 g of colorless crystalline solid. The nitrogen gas is then appropriately pressurized and accelerated by a gas pump, and heated to 140℃ by a heater before being reintroduced into the desorption device until desorption is complete. Gas chromatography-mass spectrometry analysis shows that the main component of the crystalline solid product is coumarin, with a relative content (GC peak area normalization method) of 80.02%. The gas chromatogram of the coumarin solid obtained after hot nitrogen desorption from the AB-8 type macroporous resin is attached. Figure 4 . Example 3

[0023] A solid-liquid adsorption / thermal nitrogen desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid includes the following steps: (1) At an adsorption temperature of 65℃, the cinnamon oil extraction waste liquid is brought into full contact with HZ-16 macroporous resin for 1.5h to adsorb and enrich cinnamon flavor components such as coumarin and cinnamaldehyde in the waste liquid. When the adsorption reaches saturation or after the adsorption is completed, the solid phase and liquid phase stop contacting and remove the free water of HZ-16 macroporous resin. The remaining liquid phase after adsorption is analyzed and tested and then re-adsorbed, recycled or discharged. (2) Nitrogen gas at atmospheric pressure (0.1 MPa) and a flow rate of 7.5 L / min is heated to 80°C by a heater and then introduced into a jacketed desorption device containing 44 g of HZ-16 macroporous resin saturated with fragrance components for thermal desorption. This causes most of the moisture to vaporize and desorb, and be carried away by the nitrogen gas. The desorbed mixed gas is condensed, cooled, and separated into gas and liquid phases to remove moisture. The nitrogen gas is then appropriately pressurized and accelerated by a gas pump, heated again by a heater, and reintroduced into the desorption device for thermal desorption. The nitrogen gas is recycled and reused. When the collected moisture no longer increases significantly, the nitrogen temperature is raised to 180℃ via a heater, causing the fragrance components and residual moisture to vaporize and desorb, and be carried out with the nitrogen. The desorbed mixture is condensed and cooled, and then subjected to gas-liquid-solid separation. The desorption time is 4 hours, yielding 1.5 mL of cinnamon aromatic water and 0.11 g of colorless crystalline solid. The nitrogen gas is then appropriately pressurized and accelerated by a gas pump, heated to 180℃ by a heater, and reintroduced into the desorption device until desorption is complete. Gas chromatography-mass spectrometry analysis shows that the main component of the crystalline solid product is coumarin, with a relative content (GC peak area normalization method) of 78.4%. Example 4

[0024] A solid-liquid adsorption / thermal nitrogen desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid includes the following steps: (1) At an adsorption temperature of 55℃, the cinnamon oil extraction waste liquid is brought into full contact with AB-8 macroporous resin for 1 hour to adsorb and enrich the cinnamon flavor components such as coumarin and cinnamaldehyde in the waste liquid. When the adsorption reaches saturation or after the adsorption is completed, the solid phase and liquid phase stop contacting each other and the free water of AB-8 macroporous resin is removed. The remaining liquid phase after adsorption is analyzed and tested and then re-adsorbed, recycled or discharged. (2) Nitrogen gas at atmospheric pressure (0.1 MPa) and a flow rate of 7.5 L / min is heated to 80°C by a heater and then introduced into a jacketed desorption device containing 44 g of AB-8 type macroporous resin saturated with fragrance components for thermal desorption. This causes most of the moisture to vaporize and desorb, and be carried away by the nitrogen gas. The desorbed mixed gas is condensed, cooled, and separated into gas and liquid phases to remove moisture. The nitrogen gas is then appropriately pressurized and accelerated by a gas pump, heated again by a heater, and reintroduced into the desorption device for thermal desorption. The nitrogen gas is recycled and reused. When the collected moisture no longer increases significantly, the nitrogen temperature is raised to 140℃ via a heater, causing the fragrance components and residual moisture to vaporize and desorb, and be carried out with the nitrogen. The desorbed mixture is condensed and cooled, and then subjected to gas-liquid-solid separation. The desorption time is 5 hours, yielding 2.9 mL of cinnamon aromatic water and 0.15 g of colorless crystalline solid. The nitrogen gas is then appropriately pressurized and accelerated by a gas pump, heated to 140℃ by a heater, and reintroduced into the desorption device until desorption is complete. Gas chromatography-mass spectrometry analysis shows that the main component of the crystalline solid product is coumarin, with a relative content (GC peak area normalization method) of 81.24%. Example 5

[0025] A method for the solid-liquid adsorption / superheated steam desorption separation and recovery of spice components from cinnamon oil extraction waste liquid includes the following steps: (1) At an adsorption temperature of 75℃, 44g of AB-8 type macroporous resin was fully contacted with cinnamon oil extraction waste liquid for 1 hour to adsorb and enrich cinnamon flavor components such as coumarin and cinnamaldehyde in the waste liquid. When the adsorption reached saturation or after the adsorption was completed, the macroporous resin was separated from the waste liquid. The remaining liquid phase was analyzed and tested and then re-adsorbed, recycled or discharged. (2) Superheated steam at a pressure of 0.1 MPa, a temperature of 105 °C, and a flow rate of 1.7 mL / min was introduced into a jacketed desorption device containing 44 g of AB-8 macroporous resin that had adsorbed fragrance components. This caused the moisture and fragrance components to vaporize and desorb, being carried away by the steam. The desorption time was 4 hours. The desorbed mixed gas was condensed and cooled to obtain cinnamon aromatic water. The UV absorption spectrum of the desorbate during the saturated steam desorption process of the AB-8 macroporous resin is shown in the appendix. Figure 5 . Example 6

[0026] A method for the solid-liquid adsorption / superheated steam desorption separation and recovery of spice components from cinnamon oil extraction waste liquid includes the following steps: (1) At an adsorption temperature of 55℃, 100g of HZ-16 macroporous resin was fully contacted with cinnamon oil extraction waste liquid for 1.5h to adsorb and enrich cinnamon flavoring components such as coumarin and cinnamaldehyde in the waste liquid. When the adsorption reached saturation or after the adsorption was completed, the macroporous resin was separated from the waste liquid. The remaining liquid phase was analyzed and tested and then re-adsorbed, recycled or discharged. (2) Superheated steam at a pressure of 0.1 MPa, a temperature of 140℃, and a flow rate of 780 mL / h was introduced into a jacketed desorption device containing 100 g of HZ-16 macroporous resin that had adsorbed fragrance components. This caused the moisture and fragrance components to vaporize and desorb, being carried away by the steam. The desorption time was 4 hours. The desorbed mixed gas was condensed and cooled to obtain cinnamon aromatic water. The ultraviolet absorption spectrum of the desorbed liquid during the superheated steam desorption process of the HZ-16 macroporous resin is shown in the appendix. Figure 6 In this desorption step, the desorbed mixed gas can also be introduced into the steam distillation process pipeline for cinnamon oil extraction and mixed with the distilled oil-water mixture. After condensation and cooling, the oil and water are separated, and cinnamon oil and cinnamon aromatic water are collected, thereby achieving the separation and recovery of fragrance components in the waste liquid.

Claims

1. A solid-liquid adsorption / thermal desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid, characterized in that, Includes the following steps: (1) Solid-liquid adsorption: At an adsorption operating temperature of room temperature to 100°C, the solid adsorbent is brought into full contact with the cinnamon oil extraction waste liquid to adsorb and enrich the cinnamon flavor components, including coumarin and cinnamaldehyde, in the waste liquid. The adsorption time is 0.5 to 2 hours. When the adsorption reaches saturation or after the adsorption is completed, the solid adsorbent is separated from the waste liquid. The remaining liquid phase is analyzed and tested before being re-adsorbed, recycled, or discharged. (2) Hot gas desorption: Hot gas at a certain pressure and flow rate is introduced into a jacketed heat-insulated desorption device containing a solid adsorbent that has adsorbed fragrance components for hot gas desorption, so that water and fragrance components are vaporized and released. The released mixed gas is condensed and cooled, and phase separation is performed to collect cinnamon aromatic water, cinnamon oil or crystalline solid. The crystalline solid includes coumarin crystalline solid. The hot gas refers to water vapor or hot inert gas. The hot gas pressure is less than 0.2 MPa, the temperature is 80 to 180°C, and the desorption time is 0.5 to 6 h.

2. The solid-liquid adsorption / thermal desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid according to claim 1, characterized in that, The cinnamon oil extraction waste liquid refers to the aqueous phase residue discharged from the re-distillation pot or distillation pot that also serves as a re-distillation pot during the steam distillation process of cinnamon oil extraction. The adsorption and desorption devices can be used independently or in combination, and can be operated intermittently or continuously. The phase separation operation includes gas-liquid, gas-solid, or oil-water phase separation.

3. The solid-liquid adsorption / thermal desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid according to claim 1, characterized in that, The solid-phase adsorbent is a solid-phase adsorbent material including macroporous resin, wherein the macroporous resin includes HZ-826, HZ-835, HZ-16, AB-8, and XAD-4 type macroporous resins.

4. The solid-liquid adsorption / thermal desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid according to claim 1, characterized in that, The inert gases include nitrogen and carbon dioxide at normal temperature and pressure, which can be heated to a suitable temperature by a heater to become hot inert gases. The water vapor comes from a water vapor generator and includes saturated water vapor at normal pressure and superheated water vapor at normal pressure.

5. The solid-liquid adsorption / thermal desorption separation and recovery method for spice components in cinnamon oil extraction waste liquid according to claim 1, characterized in that, The aforementioned hot gas desorption, depending on the type of hot gas used for desorption, is divided into two desorption processes: hot inert gas desorption and water vapor desorption. The specific operating steps are as follows: a. Thermal inert gas desorption: A certain flow rate of inert gas is heated to 80-100°C by a heater and then introduced into a jacketed desorption device containing a solid-phase adsorbent that has adsorbed fragrance components. This causes most of the moisture in the solid-phase adsorbent to vaporize and desorb, being carried away by the inert gas. The desorbed mixture is condensed, cooled, and the moisture is collected through phase separation. The inert gas is then appropriately pressurized and accelerated by a pump, reheated by a heater, and reintroduced into the desorption device for thermal desorption, achieving the recycling and reuse of the inert gas. When the collected moisture no longer increases significantly, the process is accelerated by adding... The heater raises the temperature of the inert gas to 100-180°C, causing the fragrance components and residual moisture to vaporize and desorb, and be carried out with the inert gas. The desorbed mixed gas is cooled by condensation and phase separation, and cinnamon aromatic water, cinnamon oil or crystalline solids are collected. The crystalline solids include coumarin crystalline solids. The cinnamon aromatic water is stored together and sold directly for application. Alternatively, it can be further separated and recovered to obtain cinnamon oil through solid-liquid adsorption / thermal gas desorption. The inert gas is appropriately pressurized and accelerated by a gas pump, and then heated by a heater before being reintroduced into the desorption device until the desorption is completed. b. Steam desorption process: Steam at a certain pressure, temperature and flow rate is introduced into a jacketed desorption device containing a solid adsorbent that has adsorbed fragrance components. The water and fragrance components adsorbed in the solid adsorbent are vaporized and desorbed and carried out by the steam. The desorbed mixed gas is condensed and cooled to obtain cinnamon aromatic water, or it is introduced into the steam distillation process pipeline for cinnamon oil extraction and mixed with the distilled oil-water mixture. After condensation and cooling and oil-water separation, cinnamon oil and cinnamon aromatic water are collected, thereby realizing the separation and recovery of fragrance components in waste liquid.

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