Method for separating fluorine-aluminum complex from tea trees
After grinding and centrifuging tea plant samples, fluorine-aluminum complexes in tea plants were separated using anion exchange columns and gradient elution. This solved the problems of poor selectivity and high separation difficulty in existing technologies, and achieved efficient and simple separation and identification of fluorine-aluminum complexes.
Patent Information
- Application Number
- CN202511023590.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-24
- Publication Date
- 2025-11-21
AI Technical Summary
Conventional methods for separating fluoride-aluminum complexes from tea plants suffer from poor selectivity, structural damage, matrix interference, and low recovery rates. Furthermore, the system formed by the roots, stems, and leaves of tea plants is not a separate aqueous solution system, making separation even more challenging.
Fresh leaves, stems, and roots of tea trees were separated by grinding, pulverizing, and centrifugation. The resulting juice was then injected into an anion exchange column for separation. Gradient elution with deionized water and sodium chloride solutions of different concentrations was used to separate anionic and cationic fluoride-aluminum complexes.
It achieves a simple and efficient separation of anion- and cation-type fluorine-aluminum complexes in tea plants, suitable for industrial use, and can separate more forms of fluorine-aluminum complexes and perform morphological identification.
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Figure CN120992301A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a method for separating fluorine-aluminum complex in tea tree, and belongs to the technical field of separation and purification. BACKGROUND
[0002] Tea tree (especially old leaves) has strong enrichment ability for fluorine and aluminum, and fluorine and aluminum are easy to form stable fluorine-aluminum complex (such as AlF3 or AlF63-) in the tea tree. At present, the methods commonly used for separating such complex mainly include the following: acid hydrolysis-ion selective electrode method (hydrolyzing the sample by heating with perchloric acid or hydrochloric acid, detecting total fluorine by fluorine ion selective electrode after releasing fluorine ions, and indirectly calculating complex fluorine), ICP-AES / ICP-MS method (dissolving the sample by nitric acid-hydrogen peroxide, measuring total aluminum and total fluorine, and speculating the complex form through the ratio), solvent extraction-spectrophotometry (extracting theaflavins-aluminum complex by using organic solvent (such as MIBK), and measuring by AlCl3 color development), column chromatography (separating the complex from tea leaf matrix by using molecular sieve or polarity difference), coagulation precipitation method (aluminum salt method, adding AlCl3 or PAC under acidic conditions to make fluorine form Al-F complex precipitate), and the like. However, these methods have problems such as poor selectivity, structure destruction, matrix interference, and low recovery rate.
[0003] Moreover, the conventional separation of fluorine-aluminum complex is in an aqueous solution system, which has few interfering substances; however, the system formed by the roots, stems and leaves of tea tree does not belong to a single aqueous solution system, and there are many kinds of organic components such as polyphenols and polysaccharides in it, which makes the separation more difficult.
[0004] Therefore, it is an urgent problem to be solved to find a method for separating fluorine-aluminum complex in tea tree. SUMMARY
[0005] [TECHNICAL PROBLEM]
[0006] The conventional method for separating fluorine-aluminum complex has problems such as poor selectivity, structure destruction, matrix interference, and low recovery rate.
[0007] The conventional method has limited separation effect and cannot separate more forms of fluorine-aluminum complex.
[0008] The system formed by the roots, stems and leaves of tea tree does not belong to a single aqueous solution system, and it is more difficult to separate.
[0009] [TECHNICAL SCHEME]
[0010] To solve the above problems, the present application provides a method for separating fluorine-aluminum complex in tea tree. Specifically, the fresh leaves, stems and roots of tea tree are ground and crushed, and centrifuged to obtain juice. Then the juice is injected into an anion exchange column for separation to obtain the forms and proportions of anionic and cationic fluorine-aluminum complexes. The method is simple, easy to operate and suitable for large-scale industrial use.
[0011] The first object of the present application is to provide a method for separating fluorine-aluminum complex in tea tree, comprising the following steps:
[0012] (1) grinding and crushing the fresh leaves, stems and roots of tea tree, and centrifuging to obtain juice;
[0013] (2) injecting the juice into an anion exchange column for elution to obtain anionic and cationic fluorine-aluminum complexes;
[0014] The elution gradient is deionized water for 1-48 min, 2% sodium chloride solution for 49-114 min, and 5% sodium chloride solution for 115-180 min.
[0015] In an embodiment of the present application, the tea tree variety in step (1) is one of Nai Bai, Zhongcha 108, Huangjin Ye and Longjing 43.
[0016] In an embodiment of the present application, the grinding in step (1) is grinding and crushing to destroy the structure.
[0017] In an embodiment of the present application, the centrifugation in step (1) is centrifugation at 3000-5000 rpm for 5-10 min.
[0018] In an embodiment of the present application, the anion exchange column in step (2) is CH-32 strong base anion exchange resin.
[0019] In an embodiment of the present application, the flow rate of the juice in step (2) is 2-2.5 mL / min.
[0020] In an embodiment of the present application, the sample injection amount in step (2) is 3-8 mL / time.
[0021] In an embodiment of the present application, the sodium chloride solution in step (2) is an aqueous sodium chloride solution.
[0022] The second object of the present application is to provide a method for simultaneously and efficiently separating anionic and cationic fluorine-aluminum complexes in tea tree, comprising the following steps:
[0023] (1) grinding and crushing the fresh leaves, stems and roots of tea tree, and centrifuging to obtain juice;
[0024] (2) Injecting the juice into an anion exchange column to elute, to obtain the anion and cation type fluorine aluminum complex;
[0025] The elution gradient is deionized water for 1-48 min, 2% sodium chloride solution for 49-114 min, and 5% sodium chloride solution for 115-180 min.
[0026] A third object of the present application is to provide a method for detecting the ratio and content of the anion and cation type fluorine aluminum complex in tea tree leaves, comprising the following steps:
[0027] (1) Grinding and crushing the fresh leaves, stems and roots of tea trees, and centrifuging to obtain juice;
[0028] (2) Injecting the juice into an anion exchange column to elute, to obtain the anion and cation type fluorine aluminum complex;
[0029] The elution gradient is deionized water for 1-48 min, 2% sodium chloride solution for 49-114 min, and 5% sodium chloride solution for 115-180 min.
[0030] [Advantages]
[0031] (1) The method of the present application is simple to operate and suitable for industrial use.
[0032] (2) The present application can effectively separate the anion and cation type fluorine aluminum complex in tea trees.
[0033] (3) The present application can separate fluorine aluminum complexes according to the difference in charge separation.
[0034] (4) The present application can separate more forms of fluorine aluminum complexes and perform morphological identification. BRIEF DESCRIPTION OF DRAWINGS
[0035] Figure 1 Test results of Examples 1-6; wherein a, b, c are the leaves of milk white tea varieties 1-3, 4-6 and 7-9 respectively; d, e, f are the leaves of Zhongcha 108 tea varieties 1-3, 4-6 and 7-9 respectively.
[0036] Figure 2 Test results of Examples 7-12; wherein a, b, c are the leaves of Huangjin tea varieties 1-3, 4-6 and 7-9 respectively; d, e, f are the leaves of Longjing 43 tea varieties 1-3, 4-6 and 7-9 respectively.
[0037] Figure 3 The anion and cation type fluorine separated from the leaves of Longjing 43 tea varieties 4-6. 19F -NMR spectrum.
[0038] Figure 4 Test results of Examples 13-16, wherein a, b, c, d are Golden Leaf, Longjing 43, Nai Bai, Zhongcha 108, respectively.
[0039] Figure 5 Test results of Examples 17-20, wherein a, b, c, d are Golden Leaf, Longjing 43, Nai Bai, Zhongcha 108, respectively.
[0040] Figure 6 Test results of Example 21; wherein the fluorine-aluminum ratios of a-e are 100 / 0, 100 / 20, 100 / 50, 100 / 100, 100 / 200, respectively. DETAILED DESCRIPTION
[0041] The preferred embodiments of the present application are described below, and it should be understood that the embodiments are for better explaining the present application, and are not used to limit the present application.
[0042] Test method:
[0043] 1. Calculation of fluorine-aluminum complex content:
[0044] The fluorine concentration in the collected eluent is determined by using a fluorine ion selective electrode, and the fluorine-aluminum complex content in the solution is calculated by multiplying the volume of the collected eluent by the fluorine concentration.
[0045] Specific operation:
[0046] Take 1 mL of the test solution and add an equal amount of TISAB buffer solution, and determine the fluorine concentration by using a fluorine electrode. The content determination formula is:
[0047] n = c x v,
[0048] Wherein, n represents the fluorine content, unit mg; c represents the concentration, unit mg / L; v represents the volume, unit L.
[0049] 2. Separation effect:
[0050] Various chemical forms of fluorine-aluminum complexes can be separated according to the charge, and cationic and anionic fluorine-aluminum complexes are separated, and verified by fluorine nuclear magnetic resonance spectrum results.
[0051] Proportion = content of anionic and cationic fluorine-aluminum complexes / total content.
[0052] Raw materials used in the examples:
[0053] Tea leaves are derived from tea trees growing vigorously, and fresh leaves are collected according to maturity and divided into 1-3, 4-6, and 7-9 leaves.
[0054] CH-32 strong base anion exchange resin: commercially available.
[0055] Sodium chloride solution: aqueous sodium chloride solution.
[0056] Example 1
[0057] A method for separating fluorine-aluminum complexes in tea trees, comprising the following steps:
[0058] (1) Fresh leaves (1-3 leaves) of the milk-white tea tree are ground by a grinder to break the structure, and centrifuged at 4000 rpm for 10 min to obtain juice;
[0059] (2) 5 mL of the juice is injected at a flow rate of 2.2 mL / min into CH-32 strong base anion exchange resin for elution to obtain negative and positive fluorine-aluminum complexes;
[0060] Among them, the elution gradient is deionized water for 1-48 min, a sodium chloride solution with a mass concentration of 2% for 49-114 min, and a sodium chloride solution with a mass concentration of 5% for 115-180 min.
[0061] Example 2
[0062] Adjust the fresh leaves (1-3 leaves) of the milk-white tea tree in step (1) of Example 1 to fresh leaves (4-6 leaves) of the milk-white tea tree, and the rest remains the same as Example 1.
[0063] Example 3
[0064] Adjust the fresh leaves (1-3 leaves) of the milk-white tea tree in step (1) of Example 1 to fresh leaves (7-9 leaves) of the milk-white tea tree, and the rest remains the same as Example 1.
[0065] Example 4
[0066] Adjust the fresh leaves (1-3 leaves) of the milk-white tea tree in step (1) of Example 1 to fresh leaves (1-3 leaves) of the medium tea 108 tea tree, and the rest remains the same as Example 1.
[0067] Example 5
[0068] Adjust the fresh leaves (1-3 leaves) of the milk-white tea tree in step (1) of Example 1 to fresh leaves (4-6 leaves) of the medium tea 108 tea tree, and the rest remains the same as Example 1.
[0069] Example 6
[0070] Adjust the fresh leaves (1-3 leaves) of the milk-white tea tree in step (1) of Example 1 to fresh leaves (7-9 leaves) of the medium tea 108 tea tree, and the rest remains the same as Example 1.
[0071] Example 7
[0072] Adjust the fresh leaves (1-3 leaves) of the milk white tea tree in step (1) of Example 1 to the fresh leaves (1-3 leaves) of the golden leaf tea tree, and keep the rest the same as Example 1.
[0073] Example 8
[0074] Adjust the fresh leaves (1-3 leaves) of the milk white tea tree in step (1) of Example 1 to the fresh leaves (4-6 leaves) of the golden leaf tea tree, and keep the rest the same as Example 1.
[0075] Example 9
[0076] Adjust the fresh leaves (1-3 leaves) of the milk white tea tree in step (1) of Example 1 to the fresh leaves (7-9 leaves) of the golden leaf tea tree, and keep the rest the same as Example 1.
[0077] Example 10
[0078] Adjust the fresh leaves (1-3 leaves) of the milk white tea tree in step (1) of Example 1 to the fresh leaves (1-3 leaves) of the Longjing 43 tea tree, and keep the rest the same as Example 1.
[0079] Example 11
[0080] Adjust the fresh leaves (1-3 leaves) of the milk white tea tree in step (1) of Example 1 to the fresh leaves (4-6 leaves) of the Longjing 43 tea tree, and keep the rest the same as Example 1.
[0081] Example 12
[0082] Adjust the fresh leaves (1-3 leaves) of the milk white tea tree in step (1) of Example 1 to the fresh leaves (7-9 leaves) of the Longjing 43 tea tree, and keep the rest the same as Example 1.
[0083] The test results are as follows:
[0084] Figure 1 The test results of Examples 1-6; wherein a, b, c are the milk white tea tree varieties 1-3, 4-6 and 7-9 leaves respectively; d, e, f are the Zhongcha 108 tea tree varieties 1-3, 4-6 and 7-9 leaves respectively.
[0085] Figure 2 The test results of Examples 7-12; wherein a, b, c are the golden leaf tea tree varieties 1-3, 4-6 and 7-9 leaves respectively; d, e, f are the Longjing 43 tea tree varieties 1-3, 4-6 and 7-9 leaves respectively.
[0086] From Figure 1 and Figure 2It can be seen that a small amount of cationic fluorine aluminum complex is separated in four tea varieties, accounting for 0.6%-18%, and there is difference among the varieties, and the cationic fluorine aluminum complex in the leaves of Zhongcha 108 tea variety accounts for the highest proportion.
[0087] The following was used 19 F-NMR was used to determine the eluent collected in the resin separation process, and the determination samples included sodium fluoride standard solution, cationic fluorine and anionic fluorine in the fluorine aluminum mixed solution, and cationic fluorine and anionic fluorine in the leaf juice of Longjing 43 tea variety.
[0088] Figure 3 The content of anionic and cationic fluorine separated from 4-6 leaves of Longjing 43 tea variety 19 F-NMR spectrum. From Figure 3 It can be seen that the chemical shift of sodium fluoride standard solution is-120.13ppm, representing free fluorine ion, and the chemical shifts of-122.23 and-120.66ppm in fluorine aluminum mixed solution and leaf juice also represent fluorine ion; only free fluorine ion and complex fluorine exist in fluorine aluminum mixed solution, therefore, the peaks with chemical shifts of-156.13 and-156.63ppm must be fluorine aluminum complex, and combined with GEOCHEM-EZ analysis, it is speculated that they represent AlF 2+ and AlF2 + respectively. In addition, the peak with chemical shift of-156.63ppm and an unlabeled small peak are detected in the cationic fluorine of tea leaf juice, which represent AlF2 + and AlF 2+ respectively.
[0089] Example 13
[0090] In step (1) of Example 1, the fresh leaves (1-3 leaves) of Nai Bai tea tree were replaced by the stems of Nai Bai tea tree, and the others were consistent with Example 1.
[0091] Example 14
[0092] In step (1) of Example 1, the fresh leaves (1-3 leaves) of Nai Bai tea tree were replaced by the stems of Zhongcha 108, and the others were consistent with Example 1.
[0093] Example 15
[0094] In step (1) of Example 1, the fresh leaves (1-3 leaves) of Nai Bai tea tree were replaced by the stems of Longjing 43, and the others were consistent with Example 1.
[0095] Example 16
[0096] In step (1) of Example 1, the fresh leaves (1-3 leaves) of Nai Bai tea tree were replaced by the stems of Huangjin Ye, and the others were consistent with Example 1.
[0097] The test results are as follows:
[0098] Figure 4 The test results of Examples 13-16 are shown in Table 2, wherein a, b, c, d are Huangjin, Longjing 43, Nai Bai, Zhongcha 108, respectively. Figure 4 It can be seen that the contents of fluorine and aluminum in the four tea tree varieties are low, and there is no obvious peak of cationic fluorine, and the curves of fluorine ions and aluminum ions do not overlap significantly, indicating that fluorine mainly exists in the form of fluorine ions in tea stems, and fluorine-aluminum complex is not the main transport form in tea stems.
[0099] Example 17
[0100] In Example 1, step (1), the fresh leaves (1-3 leaves) of Nai Bai tea tree were replaced by the roots of Nai Bai tea tree, and the others were consistent with Example 1.
[0101] Example 18
[0102] In Example 1, step (1), the fresh leaves (1-3 leaves) of Nai Bai tea tree were replaced by the roots of Zhongcha 108, and the others were consistent with Example 1.
[0103] Example 19
[0104] In Example 1, step (1), the fresh leaves (1-3 leaves) of Nai Bai tea tree were replaced by the roots of Longjing 43, and the others were consistent with Example 1.
[0105] Example 20
[0106] In Example 1, step (1), the fresh leaves (1-3 leaves) of Nai Bai tea tree were replaced by the roots of Huangjin, and the others were consistent with Example 1.
[0107] The test results are as follows:
[0108] Figure 5 The test results of Examples 17-20 are shown in Table 2, wherein a, b, c, d are Huangjin, Longjing 43, Nai Bai, Zhongcha 108, respectively. Figure 5 It can be seen that the contents of fluorine and aluminum in the four tea tree varieties are low, and there is no obvious peak of cationic fluorine, and the curves of fluorine ions and aluminum ions do not overlap significantly, indicating that fluorine mainly exists in the form of fluorine ions in tea stems, and fluorine-aluminum complex is not the main transport form in tea stems.
[0109] Comparative Example 1
[0110] In Example 11, the grinding and crushing were omitted, and the others were consistent with Example 11.
[0111] It was found that most of the plant tissues were not damaged, and the tea leaf juice could not be completely separated, which affected the final separation result.
[0112] Comparative Example 2
[0113] Adjustment was made to the elution solution in Example 11 CH-32 strong base anion exchange resin is a chlorine type anion exchange resin, and the other conditions are the same as in Example 11.
[0114] It was found that the chlorine type anion exchange resin had poor selective adsorption effect on fluorine ions, and due to the interference of other adsorbed ions, the separation effect of the fluorine aluminum complex was not good.
[0115] Comparative Example 3
[0116] The mass concentration of the sodium chloride solution eluted in Example 11 was adjusted to 2%, and the other conditions were the same as in Example 11.
[0117] It was found that the cationic fluorine aluminum complex could not be separated, and the too low mass concentration of the sodium chloride solution affected the actual separation efficiency, resulting in prolonged separation time and elongated peak shape, which could not meet the actual demand.
[0118] Comparative Example 4
[0119] The mass concentration of the sodium chloride solution eluted in Example 11 was adjusted to deionized water, and the other conditions were the same as in Example 11.
[0120] It was found that only the cationic fluorine aluminum complex could be eluted, and the adsorbed anionic fluorine aluminum complex could not be eluted, which could not achieve the separation effect.
[0121] Example 21 Verification Experiment
[0122] Sodium fluoride and aluminum sulfate were used as fluorine source and aluminum source respectively to configure standard solutions with different fluorine aluminum ratios (fluorine aluminum ratio 100 / 0, 100 / 20, 100 / 50, 100 / 100, 100 / 200; mg / L), and the standard solutions were passed into CH-32 strong base anion exchange resin, and a gradient elution method was used to separate the fluorine aluminum complex, and the eluate was collected every 6 min to determine the fluorine content and aluminum content to draw a separation graph.
[0123] The results are shown in Table 1. Figure 6 From the results, it can be seen that the CH-32 strong base anion exchange resin has good separation effect on the fluorine aluminum complex. Figure 6It can be seen that when only sodium fluoride is added, the solution only has fluoride ions with a valence of -1, at this time the fluoride ions are completely adsorbed by the resin, after being separated by elution, the peak of the anion form of fluoride on the right side is formed; when the fluorine aluminum solution with a fluorine aluminum ratio of 100 / 20 (mg / L) is added, the fluoride ions and aluminum ions in the solution form various complexes, after being separated, the fluorine aluminum complexes of the cation type on the left side and the anion type on the right side are formed, wherein the cation type contains AlF 2+ , AlF2 + and AlF3, and the anion type contains F-, AlF4 - , AlF5 2- , AlF6 3- . Through the above results, the feasibility of the method of the present application can be verified from the side.
[0124] Although the present application has been disclosed in the above with preferred embodiments, it is not intended to limit the present application, and any person skilled in the art can make various modifications and modifications without departing from the spirit and scope of the present application, therefore the protection scope of the present application should be defined by the claims.
Claims
1. A method of separating fluoroaluminium complexes in tea plants, characterised in that, It comprises the following steps: (1) grinding and crushing fresh leaves, stems and roots of tea tree, centrifuging to obtain juice; (2) injecting the juice into an anion exchange column to elute and obtain anion and cation fluorine aluminum complexes; The elution gradient is deionized water for 1-48 min, 2% sodium chloride solution for 49-114 min and 5% sodium chloride solution for 115-180 min.
2. The method of claim 1, wherein, The tea tree variety in step (1) is one of Nai Bai, Zhongcha 108, Huangjin Ye and Longjing 43.
3. The method of claim 1, wherein, The centrifugation in step (1) is at 3000-5000 rpm for 5-10 min.
4. The method of claim 1, wherein, The anion exchange column in step (2) is CH-32 strong base anion exchange resin.
5. The method of claim 1, wherein, The flow rate of the juice in step (2) is 2-2.5 mL / min.
6. The method of claim 1, wherein, The sample injection amount in step (2) is 3-8 mL / time.
7. The method of claim 1, wherein, The sodium chloride solution in step (2) is an aqueous sodium chloride solution.
8. The method of claim 1, wherein, The grinding in step (1) is grinding and crushing to destroy the structure.
9. A method for simultaneously and efficiently separating the tea plant in the shade, the type of fluorine aluminum complex is characterized by, It comprises the following steps: (1) grinding and crushing fresh leaves, stems and roots of tea tree, centrifuging to obtain juice; (2) injecting the juice into an anion exchange column to elute and obtain anion and cation fluorine aluminum complexes; The elution gradient is deionized water for 1-48 min, 2% sodium chloride solution for 49-114 min and 5% sodium chloride solution for 115-180 min.
10. A method for detecting the ratio and content of the negative and positive type of fluoroaluminum complexes in tea leaves, characterized in that, It comprises the following steps: (1) grinding and crushing fresh leaves, stems and roots of tea tree, centrifuging to obtain juice; (2) injecting the juice into an anion exchange column to elute and obtain anion and cation fluorine aluminum complexes; The elution gradient is deionized water for 1-48 min, 2% sodium chloride solution for 49-114 min and 5% sodium chloride solution for 115-180 min.