A method for extracting natural VE from deodorized distillate

Abstract

This invention belongs to the field of molecular distillation technology and discloses a method for extracting natural vitamin E from deodorized distillates, comprising the following steps: S1: component analysis and pretreatment; S2: classification of light and heavy components; S3: determination of thermodynamic properties and methods; S4: establishment of a molecular distillation separation model; S5: optimization of molecular distillation process parameters. The optimization method of this invention utilizes a specific process fitting model to quantitatively predict the impact of changes in different types of deodorized distillates, feed rates, evaporation temperatures, and operating pressures on the purity and recovery rate of vitamin E during molecular distillation separation, providing reference data for enterprises to optimize molecular distillation processes. This method helps reduce the cost of obtaining optimal process parameters, effectively reduces experimental and trial operation costs, improves work efficiency, and has significant economic benefits.

Description

Technical Field

[0001] This invention belongs to the field of molecular distillation technology, and more specifically, relates to a method for extracting natural vitamin E from deodorized distillates using molecular distillation. Background Technology

[0002] Deodorized distillate is a byproduct obtained from the deodorization or oil refining of crude vegetable oils. The main components of deodorized distillate are free fatty acids, glycerides, and some hydrocarbons. In addition, it is enriched with various bioactive substances, such as vitamin E, phytosterols, and squalene. Vitamin E (VE) is a fat-soluble vitamin and one of the most important antioxidants, possessing strong antioxidant capabilities. It is mainly found in vegetable oils, nuts, and seeds. Vitamin E protects cell membranes from free radical damage, thereby maintaining cell integrity and stability. Furthermore, vitamin E participates in regulating the function of the immune system, promoting red blood cell formation, and maintaining the normal functioning of the nervous system. Due to its unique physiological activity, vitamin E has broad application prospects in the pharmaceutical, health product, and food industries. Extracting it from deodorized distillate has significant economic value.

[0003] Molecular distillation is a continuous distillation technique that performs liquid-liquid separation under high vacuum, widely used in chemical, pharmaceutical, and food industries. Molecular distillation offers advantages such as high separation efficiency, simple operation, low energy consumption, and high product purity. It is particularly suitable for enriching or purifying high-boiling-point, high-viscosity, or heat-sensitive organic compounds, and is commonly used for the separation and purification of vitamin E. While research on molecular distillation technology is relatively mature, some issues still require optimization. For example, most molecular distillation equipment is large-scale, resulting in high economic costs and research barriers. Furthermore, due to significant differences in the content of various components in different deodorized distillates, the separation effect varies considerably when using the same equipment and process conditions to separate raw materials from different sources in industrial production. To achieve better separation results, process conditions need to be adjusted for deodorized distillates from different sources. However, in large-scale production, exploring the optimal process conditions requires significant time and cost.

[0004] Therefore, it is necessary to develop a method for quickly and conveniently obtaining process parameters. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, this invention provides a method for extracting natural vitamin E from deodorized distillates. It utilizes chemical process simulation software to perform predictive simulations of molecular distillation and provides optimization schemes for the molecular distillation process through model analysis.

[0006] The first aspect of this application is to provide a method for extracting natural vitamin E from deodorized distillates.

[0007] The specific plan is as follows:

[0008] A method for extracting natural vitamin E from deodorized distillate, comprising the following steps:

[0009] S1: Component analysis and pretreatment, component analysis of deodorized distillate, pretreatment of deodorized distillate, and component analysis again after pretreatment;

[0010] S2: Delineation of light and heavy components. Based on the proportion of each component obtained from the component analysis in step S1, and combined with the physicochemical properties of each component, they are divided into light components and heavy components.

[0011] S3: Determine thermodynamic properties and methods. Based on the target material to be separated and the properties of light and heavy components, determine the applicable thermodynamic equation through the thermodynamic equation decision diagram.

[0012] S4: Establish a molecular distillation separation model, use process simulation software to establish a separation process flow, analyze the process conditions of molecular distillation, and determine the separation process parameters; the process conditions include, but are not limited to, distillation temperature and system pressure;

[0013] S5, optimization of molecular distillation process parameters: compare the calculated results of the obtained separation process parameters with the measured values. If the difference exceeds the threshold range, the model is corrected until the difference between the calculated value and the measured value is within the threshold range.

[0014] Since the composition of deodorized distillates from different types and sources of vegetable oils varies greatly, we first take samples of the deodorized distillate for component analysis to determine the pretreatment scheme; then we perform component analysis on the pretreated deodorized distillate again to help determine the feed stream composition of the molecular distillation model.

[0015] Furthermore, the method for extracting natural vitamin E from deodorized distillate provided in this application specifically involves the steps of establishing a separation model using process simulation software and obtaining separation process parameters.

[0016] Furthermore, the measured values ​​in step S4 are obtained from measurements taken during experiments or production processes.

[0017] Further, in step S4, the simulated calculation results are compared with the measured values ​​to verify whether the actual content of natural vitamin E enriched by molecular distillation matches the simulated value predicted by the model. If the difference is large, the source of error is further analyzed to identify the main factors causing the error, and the model is corrected accordingly. The operating unit parameters in the steady-state process simulation model are adjusted, and the feed parameters corresponding to the improved process are input into the model for recalculation. Then, the verification is repeated until the expected results are achieved.

[0018] Further, step S1 includes: S11, S12 and S13;

[0019] S11: Component analysis, specifically including but not limited to the analysis of vitamin E content, sterol content, squalene content, fatty acid content, and glyceride content in deodorized distillate;

[0020] S12: Raw material pretreatment; including

[0021] Furthermore, S12 specifically includes: S121, S122, and S123;

[0022] S121: Saponification and extraction of deodorized distillate as raw material, and removal of fatty acids and glycerides to obtain saponified product - material A;

[0023] S122: After removing the solvent used for saponification from the extract and freezing crystallizing it, the sterols are separated. The residue of the extract is material B.

[0024] S123: Material B is subjected to thin-film evaporation to remove low-boiling-point components, such as aldehydes, hydrocarbons, fatty acids, etc., to obtain material C;

[0025] S13: Perform component analysis on material C.

[0026] Furthermore, in step S2, the physicochemical properties parameters include, but are not limited to, the molecular weight and boiling point of material C.

[0027] Material C was classified into heavy and light components based on its molecular weight and boiling point. The pretreated material C mainly consisted of vitamin E, most heavy component impurities, and a small amount of light component impurities. Heavy component impurities referred to glycerides and some residual oil components that were not removed during pretreatment, while light components referred to fatty acids and hydrocarbons that were not removed during pretreatment.

[0028] Further, step S3 includes obtaining the basic physicochemical properties of vitamin E, heavy component impurities, and light component impurities from the process simulation software database, and selecting a property method based on the state of the system; the system state includes the operating environment pressure and the polarity of the system.

[0029] Furthermore, the process simulation software is Aspen Plus. Aspen Plus is a widely used, easy-to-use process simulation software with a comprehensive and rich database. It is necessary to use software simulation to explore the process conditions for the molecular distillation separation of vitamin E.

[0030] The selection and determination of thermodynamic properties and methods refers to searching the Aspen Plus database for basic physical property information of vitamin E, heavy component impurities, and light component impurities, and selecting physical property methods based on the state of the system.

[0031] In one embodiment, step S4 further includes selecting representative components from a database to replace important components obtained from component analysis, thereby establishing an analytical model. Since the composition of deodorized distillates is quite complex, selecting representative components for analysis reduces the complexity of the model while ensuring effective acquisition of process parameters.

[0032] In one embodiment, a substance with a relatively large component content is selected as a representative component;

[0033] In one implementation, a single substance is selected to represent a class of substances with similar physicochemical properties;

[0034] In one implementation, oleic acid is used to replace light component impurities when establishing the analytical model;

[0035] In one implementation, trioleic acid glyceride is used to replace heavy component impurities when establishing the analytical model.

[0036] In one implementation, a flash tank in the separation unit is used to simulate the molecular distillation separation process; this reduces the computational load of the model while ensuring the accuracy of the simulation, and the simulation results are compared with the actual production results to revise the model and make it more credible.

[0037] Furthermore, the system state includes the pressure of the operating environment and the polarity of the components.

[0038] Further, in step S4, the molecular distillation separation model includes an operating unit, one feed stream and two discharge streams, a calculator module, a design specification module, and a sensitivity analysis module; the calculator module is used to control the calculation process of each operating unit; the design specification module is used to control a certain variable in the model to a specified value or a specified range; the sensitivity analysis module is used in conjunction with the design specification module to make a certain variable change within a specified range according to a preset value.

[0039] Furthermore, in step S5, the step of obtaining the calculation result includes:

[0040] S51: Input the composition and content of the raw materials as feed stream information;

[0041] S52: Set the feed rate, feed temperature, and feed pressure; set the distillation temperature and distillation pressure in the operation unit;

[0042] S53: Run the process simulation software and view the calculation results in the discharge flow stream.

[0043] Furthermore, the results obtained in step S53 are compared and verified with the measured values. If the difference between the simulation results and the measured results exceeds the set threshold, the operation unit parameters in S52 are adjusted or the model is corrected until the simulation values ​​are as close as possible to the measured values, thus obtaining the corrected and optimized model.

[0044] Furthermore, the method for correcting the model is to correct it by introducing a correction factor between the simulated temperature and the actual temperature.

[0045] Furthermore, the optimal process parameters are obtained through sensitivity analysis, and the optimal process parameters are determined by adjusting the combination of different variables.

[0046] In one implementation, the threshold for the error between the corrected experimental results and the simulation results is 5%.

[0047] The second aspect of this application is to provide an application of a method for extracting natural vitamin E from deodorized distillates, which is used in the treatment of deodorized distillates.

[0048] The simulation and optimization method in this application uses Aspen Plus software to establish a steady-state process simulation model, and performs simulation calculations and analyses on core process parameters such as distillation temperature, operating pressure, mass balance and energy balance in the process of separating vitamin E from deodorized distillate by molecular distillation.

[0049] The establishment of the steady-state process simulation model and the selection of parameters for the operating units in this application are not only applicable to the separation of VE from deodorized distillates, but can also be used to separate other active substances or remove some impurity components.

[0050] The model in this application is designed for the extraction of natural vitamin E from deodorized distillates by molecular distillation. It can quantitatively predict the impact of changes in different types of deodorized distillates, feed rates, evaporation temperatures, and operating pressures on the purity and recovery rate of vitamin E during the molecular distillation separation process, providing reference data for enterprises to optimize their molecular distillation processes.

[0051] Beneficial Effects: This invention provides a method for extracting natural vitamin E from deodorized distillates. Utilizing a specific process fitting model, it quantitatively predicts the impact of variations in different types of deodorized distillates, feed rates, evaporation temperatures, and operating pressures on the purity and recovery rate of vitamin E during molecular distillation separation. This provides reference data for enterprises to optimize molecular distillation processes. The process of extracting natural vitamin E from deodorized distillates is simulated. After establishing the model, component analysis and pretreatment are performed on different deodorized distillates. Based on the component analysis results, the components and process parameters are input into the model to obtain the final separation results. Optimal process parameters are obtained based on the results, reducing the cost of obtaining optimal process parameters, effectively reducing experimental and trial operation costs, improving work efficiency, and demonstrating significant economic benefits. Attached Figure Description

[0052] Figure 1 This is a diagram illustrating the operating unit used in the steady-state process simulation model of this invention;

[0053] Figure 2 A decision graph is selected for the physical property method of this invention;

[0054] Figure 3 The experimental results of the effect of different evaporation temperatures at 0.5 Pa on the purity of vitamin E in Example 1 of this invention are shown.

[0055] Figure 4 The simulation results show the effect of different evaporation temperatures at 0.5 Pa on the purity of vitamin E in Example 1 of this invention.

[0056] Figure 5 This is a comparison of experimental and simulation results of the effect of different evaporation temperatures at 0.5 Pa on the purity of vitamin E in Example 1 of the present invention;

[0057] Figure 6 This is a comparison between the experimental results and simulation results after adding a temperature correction factor in Example 1 of the present invention. Detailed Implementation

[0058] 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.

[0059] The purpose of this application is to predict the impact of changes in raw materials on production processes and parameters, which differs from current molecular distillation simulation studies that focus on exploring the optimal combination of process parameters.

[0060] The embodiment provides a method for extracting natural vitamin E from deodorized distillate, comprising the following steps: component analysis and pretreatment of the deodorized distillate; component simplification and classification of light and heavy components; selection and determination of thermodynamic properties and methods; process simulation of molecular distillation; and optimization of molecular distillation process parameters.

[0061] The analytical methods for each component in the deodorized distillate are as follows:

[0062] Free fatty acid content (expressed as oleic acid percentage, which is the value of acid value multiplied by 0.504);

[0063] Glyceryl ester content (high performance liquid chromatography);

[0064] Vitamin E content (GB 5009.82-2016 Determination of Sterol Composition and Total Sterols in Animal and Vegetable Oils by Gas Chromatography);

[0065] Phytosterol content (GB / T 25223-2010 Determination of Sterol Composition and Total Sterols in Animal and Vegetable Oils by Gas Chromatography).

[0066] The pretreatment steps include saponification and crystallization to remove fatty acids, glycerides, and sterols.

[0067] The pretreatment steps in this example are as follows: Saponification conditions are: reaction solvent is 2 mol / L KOH-ethanol solution (5.6 g KOH dissolved in 50 ml 95% ethanol solution), reaction time is 30 min, reaction temperature is 90 °C, and material-to-liquid ratio is 1:2. After the reaction, the mixture is extracted with n-hexane, and the supernatant is extracted. The extraction is repeated three times, and the n-hexane extracts are combined. The solvent is removed by rotary evaporation to obtain the unsaponifiable soybean deodorized distillate.

[0068] The unsaponifiables were dissolved in a crystallization solvent, specifically n-hexane, at a crystallization temperature of 4°C, a feed-to-liquid ratio of 1:6, and a crystallization time of 6 hours. Afterward, the sterols were recovered by vacuum filtration, and the solvent was removed by rotary evaporation to obtain the pretreated deodorized distillate.

[0069] Example 1: Molecular distillation simulation of soybean deodorized distillate

[0070] This embodiment uses deodorized soybean distillate as an example for pretreatment;

[0071] The first step was to determine the content of each component in the soybean deodorized distillate using the testing method described above; see Table 1.

[0072] The contents of each component in the pretreated soybean deodorized distillate were measured using the test method described above; see Table 2.

[0073] Table 1 shows the composition and content of different deodorized distillates, and Table 2 shows the composition of soybean deodorized distillate after pretreatment.

[0074] Table 1. Composition and content of soybean deodorized distillate

[0075]

[0076] Table 2 Composition and content of soybean deodorized distillate after pretreatment

[0077]

[0078] The second step involves simplifying the composition of the deodorized distillate after pretreatment, considering its still complex composition and making direct Aspen simulation difficult. Table 3 shows the simplified feed composition. Based on the fact that the actual pre-molecular distillation components consist only of vitamin E and some heavy component impurities, trioleic acid glyceride was used as the heavy component, and α-tocopherol replaced natural vitamin E as the light component in the analytical model. Since natural vitamin E includes three forms: α-tocopherol, β-tocopherol, and δ-tocopherol (α-tocopherol has the highest content, so it was used instead of vitamin E), the analytical model was established.

[0079] First, a simple molecular distillation experiment was conducted using a mixture of pure tocopherol and trioleic acid glyceride to compare the experimental results with the simulation results and determine the establishment of the model.

[0080] Table 3 Simplified feed composition

[0081]

[0082] The third step involves simulating molecular distillation. The physical property method is selected based on the polarity (or non-polarity) of the feed components and the actual operating pressure. In this example, the components are vitamin E and glycerides, both non-polar and non-electrolyte substances. Furthermore, since the separation operation is performed under high vacuum (pressure less than 10 bar), the method is chosen according to... Figure 1 and Figure 2 Based on the selection criteria, the optimal model was determined to be PENG-ROB.

[0083] Fourth, select the flash evaporation module in Aspen Plus as the separation unit for molecular distillation. The flash evaporation module includes one feed stream, one flash tank, and two discharge streams. Input the feed composition described in step two as the feed stream. After inputting the physical property parameters, component content, thermodynamic equations, and molecular distillation conditions, run the simulation. The simulated separation results can be obtained from the discharge streams, yielding simulated values ​​of the light and heavy components collected at different distillation temperatures. The process is as follows: Figure 2 As shown.

[0084] The fifth step is to compare the simulation results with the measured values ​​during the experiment to further verify whether the actual value of natural VE enrichment by molecular distillation matches the simulated value.

[0085] like Figure 3 , 4 As shown in Figure 5, the purity of vitamin E gradually decreases with increasing evaporation temperature. The trends of the simulation results and experimental results are basically consistent, but there are numerical errors.

[0086] Based on the selected flash tank separation principle and molecular distillation separation principle, the sources of error between the simulation and reality are analyzed. The distillation temperature, the main factor causing the error, is corrected to revise the model. It can be seen that the error between the corrected simulation and the actual value is less than 5%, which has high reliability.

[0087] Example 2: Molecular distillation simulation of complex components

[0088] The pretreated sample was directly subjected to molecular distillation experiments (the pretreatment method is as described above), and the separation results were simulated using the model established in Example 1.

[0089] This model was used to simulate the molecular distillation of complex components. The components were simplified according to Table 2, and the sample composition was simplified to a mixture of sterols (heavy phase), vitamin E, trioleic acid glycerides (heavy phase), and oleic acid (light phase). The simulation calculation was carried out at a distillation temperature of 180℃ and a system pressure of 0.5 Pa. The results showed that vitamin E was distilled out as a light component from the light phase. Under these conditions, the vitamin E content could be increased from 40% to 52.9%.

[0090] Table 4 Simplified feed composition and properties

[0091]

[0092] Table 5. Simulation results of combinations of oleic acid, vitamin E, trioleic acid glyceride, and sterols.

[0093]

[0094] Table 6. Results of molecular distillation experiments on the deodorized distillate after pretreatment.

[0095]

[0096] Table 7 Experimental and simulated temperatures at the same purity

[0097]

[0098] Correction factor f = T exp / T sim =180 / 211.43=0.85; Corrected purity P%=52.9%*0.85=44.97%.

[0099] Table 8 Comparison of Simulation and Experiment

[0100]

[0101]

[0102] As shown in Table 6, the simulated temperature required to achieve a purity of 42.78% in the actual molecular distillation experiment at a pressure of 0.5 Pa was 211.43 °C. The simulated temperature was too high, which is consistent with the conclusions of the pure product model. After adjusting for the temperature correction factor, the purity was 44.97%, and the simulation-experimental error was 2.19%, indicating that the molecular distillation model established using simplified components can guide actual molecular distillation.

[0103] The establishment of the steady-state process simulation model and the selection of parameters for the operating units in this application are not only applicable to the separation of VE from deodorized distillates, but can also be used to separate other active substances or remove some impurity components.

[0104] Matters not covered in this invention are common knowledge.

[0105] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method of extracting natural VE from deodorized distillate, characterized by: Comprise the following steps: S1, component analysis and pretreatment: deodorization distillate component analysis, deodorization distillate pretreatment, component analysis after pretreatment; the deodorization distillate pretreatment step specifically comprises: saponification, extraction to remove fatty acids and glycerides, frozen crystallization to separate sterols, thin film evaporation to remove low boiling point components; S2, the demarcation of light and heavy components: according to the proportion of each component obtained by step S1 component analysis combined with the physical and chemical property parameters of each component, it is divided into light component and heavy component; the physical and chemical property parameters include boiling point, molecular weight; S3, determine the thermodynamic property and method, according to the target to be separated and the physical property of light and heavy components, determine the applicable thermodynamic equation through the thermodynamic equation decision diagram; S4: establish a molecular distillation separation model, use AspenPlus software to establish a separation process flow including calculator module, design specification module, sensitivity analysis module, analyze the process conditions of molecular distillation, and determine the separation process parameters; the process conditions include but are not limited to distillation temperature, system pressure; S5, the optimization of molecular distillation process parameters, the corresponding calculation results of the obtained separation process parameters are compared with the measured values, if the difference exceeds the threshold range, a correction factor between simulated temperature and actual temperature is introduced to modify the model; the difference between the model calculation value and the measured value is within the threshold range; The component analysis specifically includes the analysis of vitamin E content, sterol content, squalene content, fatty acid content and glyceride content.

2. The process for extracting natural VE from deodorized distillate as claimed in claim 1 wherein: Step S1 includes: S12: raw material pretreatment, specifically including: S121, S122 and S123; S121: saponification and extraction are carried out with deodorization distillate as raw material, and the product after saponification-material A is obtained after removing fatty acids and glycerides; S122: after removing the solvent of the extraction liquid and freezing crystallization, sterols are separated out, and the remaining material of the extraction liquid is material B; S123: thin film evaporation is carried out on material B, and low boiling point components are removed to obtain material C; S13: component analysis is carried out on material C.

3. The process for extracting natural VE from deodorized distillate as claimed in claim 1 wherein: The step S3 includes obtaining the basic physical properties of vitamin E, heavy component impurities and light component impurities from the database of flow simulation software, and selecting the physical property method according to the state of the system; the system state includes operating environment pressure, the nature of material C.

4. The process for extracting natural VE from deodorized distillate as claimed in claim 1 wherein: In the step S4, The molecular distillation separation model includes an operation unit, one feed stream and two product streams; The design specification module is used to control a certain variable in the model to be a specified value or a specified range; The sensitivity analysis module is used to cooperate with the design specification module to change a certain variable in the specified range according to the pre-set value.

5. The process of claim 1, wherein: In the step S5, the acquisition step of the calculation result includes: S51: the composition and content of the raw material are input as the feed stream information; S52: set the feed rate, feed temperature and feed pressure; set the distillation temperature and distillation pressure in the operation unit; S53: run the flow simulation software and view the calculation results in the product stream.

6. The method for extracting natural VE from deodorization distillate according to claim 5, characterized in that: The calculation result obtained in step S53 is compared with the measured value; if the difference exceeds the threshold range, the operating unit parameters in S52 are adjusted or the model is corrected until the difference between the simulation value and the measured value is within the threshold range, and a corrected and optimized model is obtained.

7. The method of claim 6, wherein the deodorized distillate is obtained from a natural oil. The optimal process parameters are obtained through sensitivity analysis, and the optimal process parameters are determined by adjusting different combinations of variables.

8. Use of the method according to claims 1-7, characterized in that, The method is applied to the treatment of deodorized distillate.

Images