Mass transfer method in pilot scale honey refining process

Abstract

The invention provides a honey refining mass transfer method suitable for pilot scale. The method covers the whole-process mass transfer rule of normal pressure and reduced pressure processes. The method comprises the following steps: taking a pilot scale normal pressure and reduced pressure process honey refining process as an inspection object, optimizing a measurement method of physical and chemical quality attributes, and collecting physical attributes including dynamic viscosity, complex viscosity, viscous modulus and elastic modulus and chemical attributes including moisture, 5-HMF and tetrasaccharide content. The invention further provides a mass transfer kinetic equation suitable for the two processes, and a correlation model among the refined honey viscosity (eta), the moisture (S) and the temperature (T) is established, so that the mass transfer rule of the pilot scale under the normal pressure and the reduced pressure process is systematically clarified. The method disclosed by the invention provides an innovative method and theoretical reference for mass transfer research of a complex process in a traditional Chinese medicine preparation process, and has important industrial application value.

Description

Technical Field

[0001] The invention relates to the field of digitization of traditional Chinese medicine quality, and in particular to a mass transfer method in a pilot-scale honey refining process. Background Art

[0002] Honey occupies an important position in the field of traditional Chinese medicine. When mixed with medicinal powder, it not only acts as a binder and has a certain effect on the absorption and utilization of drugs, but is also a traditional Chinese medicine that can nourish the middle and moisturize dryness, and can synergize with drugs to enhance the efficacy. However, the process of refining honey for traditional Chinese medicine large honey pills has unclear mass transfer and lacks theoretical support for quality improvement, resulting in unstable quality of finished products. Therefore, the study of mass transfer in the honey refining process can be used as a key entry point to improve the quality of traditional Chinese medicine honey products. Understanding the structural characteristics of the quality attributes of the honey refining process in the real production world, clarifying the key process links and key quality attributes of the production process, and establishing an end-to-end digital quality transfer model between production processes at all levels are key contents to improve the quality and efficiency of traditional Chinese medicine manufacturing systems.

[0003] This application innovatively proposes a mass transfer method for pilot-scale honey refining process, and for the first time clarifies the mass transfer law of honey refining process under normal pressure and reduced pressure processes. It provides new guidance for the manufacturing process control of large honey pills of traditional Chinese medicine, which is crucial to improving the level of product quality control. Summary of the invention

[0004] One of the objects of the present invention is to provide a mass transfer method for a pilot scale honey refining process.

[0005] Another purpose is to provide the application of the mass transfer method of the pilot-scale honey refining process in clarifying the mass transfer law of the honey refining process of traditional Chinese medicine large honey pills.

[0006] To achieve the above object, the method comprises:

[0007] Step 1: Develop measurement methods for the physical and chemical quality attributes of honey processing;

[0008] Step 2: Collect physical and chemical quality attribute information through optimized measurement methods;

[0009] Step 3: Establishing the mass transfer mathematical relationship model of the physical and chemical quality attribute information of the atmospheric pressure and reduced pressure processes respectively;

[0010] Step 4: Combined with the above mathematical relationship model, the mass transfer law of the honey refining process under normal pressure and reduced pressure processes is clarified to achieve quality control of large honey pills of traditional Chinese medicine.

[0011] The physical quality attribute information of the present invention is pH value and rheological properties of honey, including dynamic viscosity, complex viscosity, viscous modulus and elastic modulus. The pH value is determined by measuring the sample using the operating standard of the pH meter. The measurement parameters of the rheological properties are set as follows:

[0012] (1) Rheological rotation mode measurement method: temperature step scanning is used to measure the dynamic viscosity of samples at 30°C, 40°C, 50°C, 60°C, 70°C and 80°C. The rotation mode test is a test in which the rotor continuously rotates in the sample at a certain shear stress or shear rate. The shear direction is fixed during the test. The ratio of shear stress to shear rate is the dynamic viscosity of the sample, in Pa·s. For Newtonian fluids, the shear stress and shear rate change linearly. When the test temperature is constant, the dynamic viscosity of the Newtonian fluid is a constant value. For non-Newtonian fluids, the dynamic viscosity changes with the shear rate. When the test temperature is constant, the dynamic viscosity value measured under a certain shear rate condition is the apparent viscosity of the sample.

[0013] (2) Rheological oscillation mode measurement method: temperature step scanning is used to measure the complex viscosity, viscous modulus and elastic modulus of the sample at 30℃, 40℃, 50℃, 60℃, 70℃ and 80℃. The oscillation mode test is to apply strain in the sample by the rotor with a sine wave of a certain frequency and amplitude. The shear direction changes repeatedly during the test. The total deflection amplitude is zero at the end of an oscillation cycle, and the average shear rate is also zero. During the test, the sample is subjected to oscillating shear and exerts a reaction force on the rotor. There is a phase difference between the shear stress waveform and the shear strain waveform. The viscous modulus and elastic modulus of the sample are calculated through the synchronous and asynchronous parts of the shear stress waveform and the shear strain waveform, respectively, and the unit is Pa. The viscous modulus represents the energy lost in the form of heat when the sample is deformed, reflecting the fluid properties of the sample. The elastic modulus represents the energy stored in the sample due to elastic deformation during the deformation process, reflecting the solid properties of the sample. In the oscillation mode, the sample viscosity is expressed by the modulus of complex viscosity, with the unit of Pa·s. The real part of the complex viscosity is the ratio of the viscous modulus to the strain rate, and the imaginary part is the ratio of the elastic modulus to the strain rate.

[0014] The chemical quality attribute information of the present invention is water content, 5-HMF and tetrasaccharide content, including fructose, glucose, sucrose and maltose. The specific measurement parameters are set as follows:

[0015] (1) Moisture content determination method: According to the provisions of Appendix A of SNT0852-2012 "Regulations on Inspection of Honey for Import and Export", the refractive index of honey is determined at 40°C using an Abbe refractometer to calculate the moisture content of honey.

[0016] (2) Tetrasaccharide content determination method

[0017] Preparation of test solution: Stir the uncrystallized honey sample evenly for use. Put the crystallized honey sample in a 60℃ water bath, stir evenly after all the crystals melt, and cool to room temperature for use. Weigh 80 mg of the mixed sample into a 25mL volumetric flask, add water to make up to 25mL, shake well to obtain the test solution, which is used to determine the content of tetrasaccharides in the sample.

[0018] Preparation of standard solution: Accurately weigh 96.70 mg of D-fructose, 95.70 mg of anhydrous glucose, 34.36 mg of sucrose and 31.95 mg of maltose into a 100 mL volumetric flask, add water to the volume, shake well, and obtain 0.9670 mg mL -1 D-fructose, 0.9572 mg·mL -1 Anhydrous glucose, 0.3195 mg·mL -1 Sucrose and 0.3436 mg mL -1 Maltose mixed standard solution.

[0019] Tetrasaccharide chromatographic conditions: Agilent 1260 HPLC; chromatographic column DIkma polyamino HILIC (4.6 nm × 250 mm, 5 μm); mobile phase water: acetonitrile = 30%: 70% isocratic elution; flow rate 1.0 mL min -1 ; Column temperature 30℃; Evaporative light-scattering detector (ELSD) nebulizer temperature 30℃, drift tube temperature 90℃, carrier gas flow rate 1.6SLM, carrier gas pressure 0.4MPa.

[0020] 5-HMF chromatographic conditions: Shimadzu LC-20AT high performance liquid chromatograph; chromatographic column Agilent ZORBAX SB-C18 (4.6 nm×250 mm, 5 μm); mobile phase water: methanol = 85%: 15% isocratic elution; flow rate 1.0 mL·min -1 ; Column temperature 35°C; Diode array detector (DAD) detection wavelength 284nm.

[0021] Standard curve: 1 μL, 2 μL, 4 μL, 8 μL, 10 μL and 20 μL of the tetrasaccharide mixed standard solution were injected according to the above-mentioned "tetrasaccharide chromatographic conditions" and "5-HMF chromatographic conditions", and a linear regression equation was established with the peak area as the ordinate and the content as the abscissa.

[0022] Adaptability investigation: According to the above-mentioned "tetrasaccharide chromatographic conditions", the detection limit, quantification limit, precision, repeatability, stability, recovery rate, etc. of the method were investigated.

[0023] The mathematical model of the present invention is a polynomial fitting and multivariate binomial regression mass transfer model based on physical properties and chemical properties, and the calculation steps are as follows:

[0024] Step 1: Use polynomial fitting method to establish physical and chemical single index mass transfer model of atmospheric pressure and reduced pressure process through original data;

[0025] Step 2: Establish the chemical composition structure mass transfer model of normal pressure and reduced pressure processes by using the polynomial fitting method based on the original data;

[0026] Step 3: Use the multivariate binomial regression method to establish the physical and chemical multi-index mass transfer model for normal pressure and reduced pressure processes based on the original data;

[0027] Step 4: Calculate the coefficient of determination, F value and P value of the model;

[0028] Step 5: Explain the mass transfer law based on the mass transfer model.

[0029] According to a specific embodiment of the present invention, wherein the method is applied in process control, the application is suitable for production process control of large honey pills of traditional Chinese medicine.

[0030] According to a specific embodiment of the present invention, wherein the method is used in process control, the large Chinese medicine honey pills include Tongren Niuhuang Qingxin Pills.

[0031] In summary, the present invention innovatively provides a mass transfer method for a pilot-scale honey refining process, which is suitable for process control of quality digitization.

[0032] The present invention creatively adopts and develops two mass transfer kinetic equations of the refining process, collects the physical and chemical quality attribute information of the Chinese medicine honey pill, determines the mass transfer model of the single index and chemical composition structure through polynomial fitting, and determines the multi-index mass transfer model through the multivariate binomial regression model, and finally clarifies the mass transfer law of the honey refining process, and realizes the digital quality evaluation of the Chinese medicine honey pill refining process. The established detection method of honey rheological properties is stable and reliable. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The fitting results of the mass transfer kinetic equation for the physical quality attributes of honey refining process under normal pressure process, including (a) pH, (b) dynamic viscosity and complex viscosity, (c) viscous modulus, (d) elastic modulus, (e) moisture, and (f) temperature.

[0034] Figure 2The fitting results of the mass transfer kinetic equation for chemical quality attributes of honey refining process under atmospheric pressure process, including (a) water, (b) 5-HMF, (c) fructose and glucose, (d) sucrose and maltose, (e) fructose / glucose, (f) sucrose / maltose, (g) monosaccharide / disaccharide, and (h) 5-HMF increase / water decrease.

[0035] Figure 3 The fitting results of the mass transfer kinetic equation for the physical quality attributes of honey refining process under reduced pressure process, including (a) pH, (b) dynamic viscosity and complex viscosity, (c) viscous modulus, (d) elastic modulus, (e) moisture, and (f) temperature.

[0036] Figure 4 The fitting results of the mass transfer kinetic equation for the chemical quality attributes of honey refining process under reduced pressure process. Among them, (a) water, (b) 5-HMF, (c) fructose and glucose, (d) sucrose and maltose, (e) fructose / glucose, (f) sucrose / maltose, (g) monosaccharide / disaccharide, (h) 5-HMF increase / water decrease. DETAILED DESCRIPTION

[0037] The following is further described in conjunction with the accompanying drawings and specific implementation examples, but the examples do not limit the scope of the method of the present invention.

[0038] Example 1: A pilot-scale mass transfer method for the Tongren Niuhuang Qingxin Pill honey refining process 1. Taking the normal pressure and reduced pressure honey refining processes as the research object, collecting physical and chemical quality attribute information

[0039] (1) Normal pressure refining process: 15L of honey from batch Y1 was measured and placed in a 20L honey refining tank. The temperature of the honey refining tank was set to 105-115℃ and normal pressure was applied. Samples were taken at intervals after the honey refining tank reached the set temperature. A total of 27 samples were collected. Decompression refining process: 15L of honey from batch Y2 was measured and placed in a 20L honey refining tank. The temperature of the honey refining tank was set to 50-60℃ and the vacuum degree was 0.08MPa. Samples were taken at intervals after the honey refining tank reached the set temperature. The vacuum environment needed to be released before each sampling. A total of 32 samples were collected.

[0040] (2) Optimization results of the rotational mode measurement method for rheological properties of refined honey

[0041] In 40S -1 , 50S -1 、60S -1 , 70S -1 , 80S -1 、90S -1 and 100S -1The dynamic viscosity of refined honey was measured under shear rate, and linear regression was performed with dynamic viscosity as Y and shear rate as X. The regression equation was Y = 8.6223-0.0031X, R 2 =0.9978. The research results show that honey refining in 40 ~ 100S -1 Within the shear rate range, the dynamic viscosity has a high correlation with the shear rate, which can stably characterize the dynamic viscosity of refined honey. Therefore, the shear rate of 50S is selected. -1 Measuring the dynamic viscosity of refined honey rheology.

[0042] (3) Optimization results of the oscillation mode measurement method for rheological properties of refined honey

[0043] The shear frequency directly affects the measurement results of the rheological oscillation mode of refined honey. The complex viscosity of refined honey and combined honey changes linearly in the shear frequency range of 4 to 6 Hz. Therefore, the shear frequency is selected as 5 Hz. In the shear strain range of 40 to 60%, the complex viscosity of raw honey fluctuates less, and the complex viscosity of refined honey changes linearly. Therefore, the shear strain of 50% and the shear frequency of 5 Hz are selected to measure the complex viscosity, viscous modulus and elastic modulus in the rheological properties of refined honey.

[0044] (4) Optimization results of measurement temperature for rheological properties of refined honey

[0045] At 30℃, 40℃, 50℃, 60℃, 70℃ and 80℃, the RSD of dynamic viscosity of refined honey was 41.80%, 36.00%, 31.70%, 27.64%, 24.53%, 21.80%, the RSD of complex viscosity was 41.65%, 36.02%, 31.33%, 27.15%, 23.29%, 19.86%, the RSD of viscous modulus was 41.66%, 36.03%, 31.40%, 27.60%, 24.83%, 21.90%, and the RSD of elastic modulus was 58.11%, 48.55%, 45.56%, 24.63%, 28.94%, 26.75%. Therefore, 30℃ was selected as the measurement temperature of honey rheology.

[0046] 2. Establishment of mass transfer kinetic equations and clarification of mass transfer laws in atmospheric pressure process

[0047] (1) Mass transfer kinetic equations and laws of physical quality properties of honey refining process under normal pressure

[0048] The fitting results of mass transfer kinetic equation are shown in Figure 1(a)-(d), the model equation is shown in Table 1. Among them, pH is affected by many factors. First, heating leads to a decrease in volatile acidic components such as acetic acid, and the pH rises. The phenolic acid substances are produced during the honey refining process, and the pH decreases. Finally, the water content decreases rapidly, the degree of ionization of acidic substances decreases, and the pH increases. In addition, the dynamic equations of dynamic viscosity, complex viscosity and viscous modulus in rheology at 30°C are basically consistent, showing an overall upward trend, which is opposite to the change trend of elastic modulus.

[0049] Furthermore, the fitting results of dynamic viscosity-water-temperature are shown in Figure 1 (e)-(f), the results show that the binomial fitting results of dynamic viscosity, water content and temperature are all good. The multivariate binomial regression was used to establish the correlation model of refined honey viscosity (η), water content (S) and temperature (T), and the regression equation is ln (η) = 15.94-0.7583S-0.1807T+0.0075S 2 +0.0004T 2 +0.0031ST,R 2 =0.9991. In addition, the regression equation is simplified, and the regression equation of the viscosity and water content of refined honey at 30°C is ln(η)=10.89-0.6641S+0.0075S 2 The research results show that in the process of refining honey under normal pressure, the change of dynamic viscosity can be characterized by the water dynamics equation.

[0050] (2) Mass transfer kinetic equations and laws of chemical quality properties in the atmospheric pressure honey refining process

[0051] The fitting results of mass transfer kinetic equation are shown in Figure 2 (a)-(d), the model equation is shown in Table 1. Among them, the water content continues to decrease, and the rate of decrease gradually increases, 5-HMF continues to increase, and the rate of decrease also gradually increases. In addition, fructose, glucose and sucrose in the tetrasaccharide participate in the Maillard reaction during the refining process, and the content decreases. At the same time, due to the decrease in water content, the overall trend is upward, and maltose continues to increase during the refining process. Further, the mass transfer kinetic equation fitting results of the chemical property composition structure are shown in Figure 2 (e)-(h), the results show that fructose / glucose continued to decrease during the honey refining process, indicating that the Maillard reaction rate of fructose>glucose, sucrose / maltose first decreased and then remained basically unchanged, indicating that the decomposition rate of sucrose>maltose, and monosaccharides / disaccharides were affected by the decrease in water content and showed an overall downward trend. In addition, the increase in 5-HMF / decrease in water content first increased and then decreased, reaching the highest at around 170 minutes, which was consistent with the time point when the water content decrease rate increased, indicating that there was no obvious linear correlation between the increase rate of 5-HMF and the water content decrease rate, and the kinetic equations of the two were independent of each other. Therefore, the Maillard reaction rate of fructose>glucose.

[0052] Table 1 Mass transfer kinetic equations for physical and chemical quality attributes of honey refining process under atmospheric pressure

[0053]

[0054]

[0055] Note: X is the honey refining time, and “-” means no such item.

[0056] 3. Establishment of the mass transfer kinetic equation of decompression process and clarification of the mass transfer law

[0057] (1) Mass transfer kinetic equations and laws of physical quality properties in honey refining process using decompression technology

[0058] The fitting results of mass transfer kinetic equation are shown in Figure 3 (a)-(d), the model equation is shown in Table 2. Among them, different from the normal pressure process, the pH of the reduced pressure process is mainly affected by the decrease of water content, and the pH continues to increase. In addition, the elastic modulus remains basically unchanged during the reduced pressure process, while the dynamic equations of dynamic viscosity, complex viscosity and viscous modulus are basically the same.

[0059] Furthermore, the fitting results of dynamic viscosity-water-temperature are shown in Figure 3 (e)-(f). Multivariate binomial regression was used to establish the correlation model between molten honey viscosity (η), water content (S) and temperature (T). The regression equation is ln(η)=15.14-0.7088S-0.1832T+0.0065S 2 +0.0004T 2 +0.0033ST,R 2 =0.9993. After simplification, the regression equation at 30°C is ln(η)=9.66-0.6086S+0.0065S 2 The results show that in the process of honey refining by reduced pressure technology, the change of dynamic viscosity can also be characterized by the water dynamics equation.

[0060] (2) Mass transfer kinetic equations and laws of chemical quality properties in honey refining process using vacuum technology

[0061] The fitting results of the mass transfer kinetic equation of chemical properties in the honey refining process under reduced pressure are shown in Figure 4 (a)-(d), the model equation is shown in Table 2. The moisture content continued to decrease, and the rate of decrease remained basically unchanged, while 5-HMF continued to increase, but the rate of increase gradually decreased. The results showed that the kinetic equations of moisture content and 5-HMF in the decompression process of honey refining were independent of each other. In addition, the study found that the tetrasaccharides showed an overall increasing trend, with the rate of increase of glucose being greater than that of fructose, and the rate of increase of maltose being greater than that of sucrose.

[0062] Furthermore, the mass transfer kinetic equation fitting results of the chemical properties and composition structure of the honey refining process under reduced pressure are shown in Figure 4 (e)-(h), the model equation is shown in Table 2. The results show that the change trends of fructose / glucose, sucrose / maltose, and monosaccharides / disaccharides are basically consistent with the normal pressure honey refining process, and show an overall downward trend, indicating that temperature is the key factor affecting the Maillard reaction rate in the honey refining process.

[0063] Table 2 Kinetic equations of mass transfer of physical and chemical properties during honey refining by decompression process

[0064]

[0065]

[0066] Note: X is the honey refining time, and “-” means no such item.

[0067] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A mass transfer method for a pilot scale honey refining process, characterized in that: The method covers the mass transfer law of the honey refining process of atmospheric pressure and reduced pressure process at pilot production scale, determines the decisive factors of quality change in the honey refining process through comprehensive analysis of physical and chemical quality attributes, and optimizes key process parameters. The method comprises the following steps: Step 1: Collect the physical quality attribute information of honey during the normal pressure and reduced pressure refining processes; Step 2: Collect the chemical quality attribute information of honey during the normal pressure and reduced pressure refining processes; Step 3: Establish mass transfer kinetic equations for physical and chemical quality attributes for atmospheric and reduced pressure processes; Step 4: Explain the mass transfer laws of normal pressure and reduced pressure processes, and determine the key process parameters that affect the quality of honey refining.

2. The method according to claim 1, characterized in that The physical quality property information in step 1 is rheological properties, wherein the rheological properties include dynamic viscosity, complex viscosity, viscous modulus, and elastic modulus.

3. The method according to claim 1, characterized in that The chemical quality attribute information in step 2 is pH value and moisture content, 5-HMF content and tetrasaccharide content, including the specific composition ratio of fructose, glucose, sucrose and maltose.

4. The method according to claim 2, characterized in that: Collecting physical quality attribute information in step 1 includes the following steps: Step 1.1: Determine the pH value of the sample according to the operating standard of the pH meter to characterize the acidity of the honey; Step 1.2: Establish a method for measuring the rheological properties of refined honey and optimize the measurement accuracy through rotation and oscillation modes; Step 1.3: Obtain rheological properties according to the optimized measurement method, including dynamic viscosity, complex viscosity, viscous modulus and elastic modulus.

5. The method according to claim 4, characterized in that The rheological property measurement method in step 1.2 includes: In the rotation mode, the measurement of dynamic viscosity is optimized by linear regression fitting. In the oscillation mode, the measurement of complex viscosity, viscous modulus and elastic modulus is optimized by using the linear variation law of shear frequency and shear strain. The measurement temperature is optimized by calculating the relative standard deviation (RSD) at different temperatures.

6. The method according to claim 3, characterized in that Collecting chemical quality attribute information in step 2 includes the following steps: Step 2.1: According to the moisture determination standard in the "Regulations for Inspection of Import and Export Honey" SNT0852-2012, use an Abbe refractometer to measure the refractive index of honey at 40°C and calculate the moisture content; Step 2.2: Establish a method for determining the content of 5-hydroxymethylfurfural (5-HMF) and tetrasaccharides in refined honey, and measure the contents of 5-HMF, fructose, glucose, sucrose and maltose, respectively.

7. The method according to claim 1, characterized in that The methods for establishing the mass transfer kinetic equations of the physical and chemical quality attributes of the atmospheric and reduced pressure processes in step 3 are the polynomial fitting method and the multivariate binomial regression mathematical model, and the specific model parameters are optimized according to different process conditions.

8. Application of the mass transfer method of the pilot-scale honey refining process according to any one of claims 1 to 7 in the production process control of large honey pills of traditional Chinese medicine, characterized in that: The method realizes intelligent quality monitoring and process optimization by real-time monitoring of the physical and chemical properties of the honey refining process, thereby improving production efficiency and product quality consistency.

Images