Method for extracting chlorogenic acid from pepper meal
By using acidic polar solvent extraction and stepwise pH adjustment, chlorogenic acid is efficiently extracted from Sichuan pepper meal, solving the problems of low extraction efficiency and high cost in existing technologies, and realizing the production of high-purity, low-cost chlorogenic acid.
Patent Information
- Application Number
- CN202511299008.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-11
- Publication Date
- 2025-11-14
AI Technical Summary
Existing methods for extracting chlorogenic acid from Sichuan pepper meal are not efficient enough and lack environmentally friendly extraction processes, resulting in high production costs.
The pith of Sichuan pepper was extracted using an acidic polar solvent. Chlorogenic acid was extracted and purified by adjusting the pH value stepwise, adding calcium chloride solution for precipitation, and combining this with a hydrolysis step.
It achieves efficient extraction of chlorogenic acid with an extraction rate of ≥98% and a total yield of ≥90%, resulting in high product purity, low cost, and environmental friendliness.
Smart Images
Figure CN120943731A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of plant extraction technology, specifically relating to a method for extracting chlorogenic acid from Sichuan pepper meal. Background Technology
[0002] Chlorogenic acid is a phenolic acid formed from caffeic acid and quinic acid. It is a phenylpropanoid compound produced by plants during aerobic respiration via the shikimic acid pathway. Chlorogenic acid has antibacterial, antiviral, white blood cell-boosting, hepatoprotective, choleretic, antitumor, blood pressure-lowering, blood lipid-lowering, free radical scavenging, and central nervous system-stimulating effects, and is widely used in medicine, health products, cosmetics, and other fields.
[0003] Currently, the main commercial sources of chlorogenic acid are extracts from plant materials such as Eucommia, Caprifoliaceae, and Asteraceae plants, with high concentrations found in Eucommia leaves, dandelion, honeysuckle, and tobacco leaves. However, methods for extracting chlorogenic acid from these common plants are already well-established, leading to intense market competition. Therefore, finding new raw materials and efficient extraction methods for chlorogenic acid is of significant practical importance.
[0004] Sichuan pepper is a common seasoning and also a traditional Chinese medicine with effects such as warming the stomach and relieving pain, killing insects and relieving itching. Sichuan pepper contains various bioactive components, such as volatile oils, alkaloids, and flavonoids. Studies have found that Sichuan pepper also contains a certain amount of chlorogenic acid. After supercritical extraction of Sichuan pepper essential oil and oleoresin, chlorogenic acid is concentrated in the Sichuan pepper meal, which is inexpensive and an ideal source of chlorogenic acid. However, there are currently few reports on methods for extracting chlorogenic acid from Sichuan pepper meal. Summary of the Invention
[0005] The purpose of this invention is to provide a method for extracting chlorogenic acid from Sichuan pepper meal, which can extract chlorogenic acid from Sichuan pepper meal efficiently and in an environmentally friendly manner, thereby reducing production costs.
[0006] To achieve the above-mentioned objectives, the technical solution of the present invention is as follows: A method for extracting chlorogenic acid from Sichuan pepper meal includes the following steps: (1) Extract the pepper meal with an acidic polar solvent, concentrate the extract to remove the solvent, and centrifuge to remove the precipitate to obtain chlorogenic acid extract; the polar solvent is one or more of methanol, ethanol, acetone and their aqueous solutions; (2) Gradually increase the pH value of the chlorogenic acid extract step by step. After each step of pH adjustment, add calcium chloride solution and separate the precipitate. (3) Add a strong acid solution to the precipitate for hydrolysis, and dry the hydrolysate to obtain chlorogenic acid.
[0007] Furthermore, the pepper meal is pepper from which pepper essential oil and pepper oleoresin have been extracted.
[0008] Furthermore, in step (1), sulfuric acid, hydrochloric acid, or phosphoric acid is added to adjust the pH value of the polar solvent to 2-4.
[0009] Furthermore, in step (1), the volume-to-mass ratio of polar solvent to pepper meal is (3-5):1L / kg, the extraction temperature is 40-60℃, the extraction is performed 3-5 times, and each extraction lasts 0.5-1.5h.
[0010] Furthermore, in step (2), sodium bicarbonate or sodium carbonate is added to the chlorogenic acid extract in three steps to gradually increase the pH value.
[0011] Furthermore, in step (2), the pH value is adjusted to 4-5 in step 1, to 7-8 in step 2, and to 8-9 in step 3. After each step of pH adjustment, calcium chloride solution is added until no more precipitate is produced. After centrifugation to separate the precipitate, the next step of pH adjustment is carried out.
[0012] Furthermore, in step (3), one or more of sulfuric acid, hydrochloric acid or phosphoric acid are used to adjust the initial hydrolysis system to a pH of 2 to 4, the hydrolysis temperature to 50 to 70°C, and the hydrolysis time to 3 to 6 hours.
[0013] Furthermore, in step (3), the precipitate obtained by adjusting the pH value in step 2 is hydrolyzed separately, while the precipitates obtained by adjusting the pH value in steps 1 and 3 are hydrolyzed together.
[0014] Furthermore, in step (3), the chlorogenic acid content obtained by hydrolyzing the precipitate obtained by adjusting the pH value in step 2 is ≥10%, and the content yield is ≥70%; the chlorogenic acid content obtained by hydrolyzing the precipitates obtained by adjusting the pH value in steps 1 and 3 together is 1-5%.
[0015] Furthermore, in step (1), the chlorogenic acid extraction rate is ≥98%; in step (3), the total chlorogenic acid content yield is ≥90%.
[0016] The chlorogenic acid mentioned in this invention refers to a mixture of chlorogenic acid (3-caffeoylquinic acid), cryptochlorogenic acid (4-caffeoylquinic acid), and neochlorogenic acid (5-caffeoylquinic acid).
[0017] The beneficial effects of this invention are at least as follows: 1. Wide range of raw material sources: Sichuan pepper is a common seasoning and traditional Chinese medicine with abundant resources. The remaining Sichuan pepper meal after supercritical extraction of the main components, Sichuan pepper essential oil and Sichuan pepper oleoresin, is inexpensive, providing a new source of raw materials for the extraction of chlorogenic acid.
[0018] 2. High extraction efficiency: Acidic polar solvent extraction can effectively extract chlorogenic acid from pepper meal, with an extraction rate of ≥98% in the polar solvent extraction stage; the total yield of chlorogenic acid in the three-step precipitation is ≥90%.
[0019] 3. High product purity: By adjusting the pH value stepwise and adding calcium chloride precipitation, impurities can be effectively removed, improving the purity of chlorogenic acid. The chlorogenic acid content obtained after hydrolysis of the second-step precipitation is ≥10%, with a yield ≥70%.
[0020] 4. Environmentally friendly and pollution-free: This invention does not use toxic or harmful organic solvents, making it environmentally friendly.
[0021] 5. Low cost: The extraction process of this invention is simple and easy to operate, requiring no complex equipment or expensive reagents, resulting in low production costs. Attached Figure Description
[0022] Figure 1 This is the liquid phase spectrum of Example 1 of the present invention. Detailed Implementation
[0023] Example 1
[0024] This embodiment provides a method for extracting chlorogenic acid from Sichuan pepper meal, the steps of which are as follows: (1) Acidic polar solvent extraction: 100 kg of pepper pulp from which pepper essential oil and pepper oleoresin were extracted by supercritical extraction was placed in an extraction tank, and 400 L of 70% ethanol aqueous solution was added. The pH was adjusted to 2 with hydrochloric acid, and the extraction was carried out 4 times at 60℃, each extraction lasting 0.5 h. The obtained extracts were combined and concentrated, and the precipitate was removed by centrifugation to obtain 105 kg of chlorogenic acid extract.
[0025] (2) pH adjustment and precipitation separation: Sodium bicarbonate was added to the chlorogenic acid extract to raise the pH value in three steps. Step 1: Adjust to pH 5, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 2: Adjust to pH 8, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 3: Adjust to pH 9, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate.
[0026] (3) Hydrolysis and drying: The precipitate from step 2 was added separately to hydrochloric acid solution, the initial pH of the hydrolysis system was adjusted to 2, and hydrolysis was carried out at 50°C for 3 hours; the precipitates from steps 1 and 3 were combined and added to hydrochloric acid solution, the initial pH of the hydrolysis system was adjusted to 2, and hydrolysis was carried out at 50°C for 3 hours. The hydrolysate was concentrated and dried to obtain chlorogenic acid.
[0027] The extraction rate of chlorogenic acid in step (1) was 98.2%. In step (3), the chlorogenic acid content obtained after hydrolyzing the precipitate in step 2 alone was 10.5%, with a content yield of 72.0%; the chlorogenic acid content obtained after hydrolyzing the precipitates in steps 1 and 3 together was 2.5%, with a content yield of 19.7%.
[0028] In this embodiment, the total yield of chlorogenic acid was 91.7%. Example 2
[0029] This embodiment provides a method for extracting chlorogenic acid from Sichuan pepper meal, the steps of which are as follows: (1) Acidic polar solvent extraction: 100 kg of pepper pulp from which pepper essential oil and pepper oleoresin were extracted by supercritical extraction was placed in an extraction tank, 300 L of 98% methanol was added, the pH was adjusted to 3 with sulfuric acid, and the extraction was carried out 5 times at 50℃ for 1 hour each time. The obtained extracts were combined and concentrated, and the precipitate was removed by centrifugation to obtain 108 kg of chlorogenic acid extract.
[0030] (2) pH adjustment and precipitation separation: Sodium carbonate was added to the chlorogenic acid extract to raise the pH value in three steps. Step 1: Adjust to pH 4.3, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 2: Adjust to pH 7.5, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 3: Adjust to pH 8.5, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate.
[0031] (3) Hydrolysis and drying: The precipitate from step 2 was added separately to a sulfuric acid solution, and the initial pH of the hydrolysis system was adjusted to 3.1. Hydrolysis was carried out at 60°C for 5 hours. The precipitates from steps 1 and 3 were combined and added to a hydrochloric acid solution, and the initial pH of the hydrolysis system was adjusted to 3. Hydrolysis was carried out at 60°C for 5 hours. The hydrolysate was concentrated and dried to obtain chlorogenic acid.
[0032] The extraction rate of chlorogenic acid in step (1) was 98.0%. In step (3), the chlorogenic acid content obtained after hydrolyzing the precipitate in step 2 alone was 10.7%, with a content yield of 73.4%; the chlorogenic acid content obtained after hydrolyzing the precipitates in steps 1 and 3 together was 2.3%, with a content yield of 17.5%.
[0033] In this embodiment, the total yield of chlorogenic acid was 90.9%. Example 3
[0034] This embodiment provides a method for extracting chlorogenic acid from Sichuan pepper meal, the steps of which are as follows: (1) Acidic polar solvent extraction: 100 kg of pepper pomace from which pepper essential oil and pepper oleoresin were extracted by supercritical extraction was placed in an extraction tank, and 500 L of acetone aqueous solution with a volume fraction of 80% was added. The pH was adjusted to 4 with phosphoric acid, and the extraction was carried out 3 times at 40℃, each extraction lasting 1.5 h. The obtained extracts were combined and concentrated, and the precipitate was removed by centrifugation to obtain 98 kg of chlorogenic acid extract.
[0035] (2) pH adjustment and precipitation separation: Sodium bicarbonate was added to the chlorogenic acid extract to raise the pH value in three steps. Step 1: Adjust to pH 4, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 2: Adjust to pH 7, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 3: Adjust to pH 8, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate.
[0036] (3) Hydrolysis and drying: The precipitate from step 2 was added separately to a phosphoric acid solution, the initial pH of the hydrolysis system was adjusted to 4, and hydrolysis was carried out at 70°C for 6 hours; the precipitates from steps 1 and 3 were combined and added to a phosphoric acid solution, the initial pH of the hydrolysis system was adjusted to 4, and hydrolysis was carried out at 70°C for 6 hours. The hydrolysate was concentrated and dried to obtain chlorogenic acid.
[0037] The extraction rate of chlorogenic acid in step (1) was 98.5%. In step (3), the chlorogenic acid content obtained after hydrolyzing the precipitate in step 2 alone was 10.1%, with a content yield of 70.1%; the chlorogenic acid content obtained after hydrolyzing the precipitates in steps 1 and 3 together was 2.6%, with a content yield of 20.3%.
[0038] In this embodiment, the total yield of chlorogenic acid was 90.4%. Example 4
[0039] This embodiment provides a method for extracting chlorogenic acid from Sichuan pepper meal, the steps of which are as follows: (1) Acidic polar solvent extraction: 100 kg of pepper pomace from which pepper essential oil and pepper oleoresin were extracted by supercritical extraction was placed in an extraction tank, and 400 L of a 1:1 mixed aqueous solution of ethanol and methanol with a volume fraction of 80% was added. The pH was adjusted to 3 with a 1:1 mixed acid of hydrochloric acid and phosphoric acid. The extraction was carried out 4 times at 50℃, with each extraction lasting 1 h. The obtained extracts were combined and concentrated, and the precipitate was removed by centrifugation to obtain 110 kg of chlorogenic acid extract.
[0040] (2) pH adjustment and precipitation separation: Sodium carbonate was added to the chlorogenic acid extract to raise the pH value in three steps. Step 1: Adjust the pH to 4.5, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 2: Adjust the pH to 7.6, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 3: Adjust the pH to 8.5, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate.
[0041] (3) Hydrolysis and drying: The precipitate from step 2 was added separately to a 1:1 mixed acid solution of hydrochloric acid and phosphoric acid, and the initial pH of the hydrolysis system was adjusted to 3. Hydrolysis was carried out at 60°C for 4.5 h. The precipitates from steps 1 and 3 were combined and added to a 1:1 mixed acid solution of hydrochloric acid and phosphoric acid, and the initial pH of the hydrolysis system was adjusted to 3. Hydrolysis was carried out at 60°C for 4.5 h. The hydrolysates were concentrated and dried to obtain chlorogenic acid.
[0042] The extraction rate of chlorogenic acid in step (1) was 98.3%. In step (3), the chlorogenic acid content obtained after hydrolyzing the precipitate in step 2 alone was 10.5%, with a content yield of 72.6%; the chlorogenic acid content obtained after hydrolyzing the precipitates in steps 1 and 3 together was 2.4%, with a content yield of 18.2%.
[0043] In this embodiment, the total yield of chlorogenic acid was 90.8%. Example 5
[0044] This embodiment provides a method for extracting chlorogenic acid from Sichuan pepper meal, the steps of which are as follows: (1) Acidic polar solvent extraction: 100 kg of pepper pomace from which pepper essential oil and pepper oleoresin were extracted by supercritical extraction was placed in an extraction tank, and 400 L of a 1:1:1 mixed aqueous solution of ethanol, methanol and acetone with a volume fraction of 80% was added. The pH was adjusted to 3 with a 1:1:1 mixed acid of hydrochloric acid, sulfuric acid and phosphoric acid. The extraction was carried out 4 times at 50℃, with each extraction lasting 1 h. The obtained extracts were combined and concentrated, and the precipitate was removed by centrifugation to obtain 106 kg of chlorogenic acid extract.
[0045] (2) pH adjustment and precipitation separation: Sodium carbonate was added to the chlorogenic acid extract to raise the pH value in three steps. Step 1: Adjust to pH 4.5, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 2: Adjust to pH 7.5, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate; Step 3: Adjust to pH 8.4, add calcium chloride solution until no more precipitation is produced, and centrifuge to separate the precipitate.
[0046] (3) Hydrolysis and drying: The precipitate from step 2 was added separately to a 1:1 mixed acid solution of hydrochloric acid and phosphoric acid, and the initial pH of the hydrolysis system was adjusted to 3. Hydrolysis was carried out at 58°C for 5 hours. The precipitates from steps 1 and 3 were combined and added to a 1:1 mixed acid solution of hydrochloric acid and phosphoric acid, and the initial pH of the hydrolysis system was adjusted to 3. Hydrolysis was carried out at 58°C for 5 hours. The hydrolysates were concentrated and dried to obtain chlorogenic acid.
[0047] The extraction rate of chlorogenic acid in step (1) was 98.5%. In step (3), the chlorogenic acid content obtained after hydrolyzing the precipitate in step 2 alone was 10.4%, with a content yield of 70.6%; the chlorogenic acid content obtained after hydrolyzing the precipitates in steps 1 and 3 together was 2.5%, with a content yield of 19.7%.
[0048] In this embodiment, the total yield of chlorogenic acid was 90.3%. Comparative Example 1
[0049] The only difference between this comparative example and Example 1 is that hydrochloric acid was not added to adjust the pH value during the acidic polar solvent extraction process in step (1).
[0050] The extraction rate of chlorogenic acid in step (1) was 95.7%. In step (3), the chlorogenic acid content obtained after hydrolyzing the precipitate in step 2 alone was 8.5%, with a content yield of 53.2%; the chlorogenic acid content obtained after hydrolyzing the precipitates in steps 1 and 3 together was 4.3%, with a content yield of 35.1%.
[0051] The total yield of chlorogenic acid in this comparative example was 88.3%. Comparative Example 2
[0052] The only difference between this comparative example and Example 1 is that in step (2), the pH value is adjusted step by step during the precipitation separation process, and sodium carbonate is added to directly adjust the pH value to 9.
[0053] The extraction rate of chlorogenic acid in step (1) was 98.3%. The chlorogenic acid content obtained after precipitation and hydrolysis in step (3) was 5.6%, with a content recovery rate of 91.5%.
Claims
1. A method for extracting chlorogenic acid from Sichuan pepper meal, characterized in that, Includes the following steps: (1) Extract the pepper meal with an acidic polar solvent, concentrate the extract to remove the solvent, and centrifuge to remove the precipitate to obtain chlorogenic acid extract; the polar solvent is one or more of methanol, ethanol, acetone and their aqueous solutions; (2) Gradually increase the pH value of the chlorogenic acid extract step by step. After each step of pH adjustment, add calcium chloride solution and separate the precipitate. (3) Add a strong acid solution to the precipitate for hydrolysis, and dry the hydrolysate to obtain chlorogenic acid.
2. The method for extracting chlorogenic acid from Sichuan pepper meal according to claim 1, characterized in that, The pepper meal is made from pepper from which pepper essential oil and pepper oleoresin have been extracted.
3. The method for extracting chlorogenic acid from Sichuan pepper meal according to claim 1, characterized in that, In step (1), sulfuric acid, hydrochloric acid or phosphoric acid are added to adjust the pH value of the polar solvent to 2 to 4.
4. The method for extracting chlorogenic acid from Sichuan pepper meal according to claim 1, characterized in that, In step (1), the volume-to-mass ratio of polar solvent to pepper meal is (3-5):1L / kg, the extraction temperature is 40-60℃, the extraction is performed 3-5 times, and each extraction lasts 0.5-1.5h.
5. The method for extracting chlorogenic acid from Sichuan pepper meal according to claim 1, characterized in that, In step (2), sodium bicarbonate or sodium carbonate is added to the chlorogenic acid extract in three steps to gradually increase the pH value.
6. The method for extracting chlorogenic acid from Sichuan pepper meal according to claim 5, characterized in that, In step (2), the pH value is adjusted to 4-5 in step 1, to 7-8 in step 2, and to 8-9 in step 3. After each pH adjustment, calcium chloride solution is added until no more precipitate is produced. After centrifugation to separate the precipitate, the next pH adjustment is carried out.
7. The method for extracting chlorogenic acid from Sichuan pepper meal according to claim 1, characterized in that, In step (3), the initial pH of the hydrolysis system is adjusted to 2-4 using one or more of sulfuric acid, hydrochloric acid, or phosphoric acid, the hydrolysis temperature is 50-70℃, and the hydrolysis time is 3-6h.
8. The method for extracting chlorogenic acid from Sichuan pepper meal according to claim 6, characterized in that, In step (3), the precipitate obtained by adjusting the pH value in step 2 of step (2) is hydrolyzed separately, while the precipitates obtained by adjusting the pH value in steps 1 and 3 are hydrolyzed together.
9. The method for extracting chlorogenic acid from Sichuan pepper meal according to claim 8, characterized in that, In step (3), the chlorogenic acid content obtained by hydrolyzing the precipitate obtained by adjusting the pH value in step (2) separately is ≥10%, and the content yield is ≥70%; the chlorogenic acid content obtained by hydrolyzing the precipitates obtained by adjusting the pH value in steps 1 and 3 together is 1-5%.
10. The method for extracting chlorogenic acid from Sichuan pepper meal according to any one of claims 1-9, characterized in that, In step (1), the chlorogenic acid extraction rate is ≥98%; in step (3), the total chlorogenic acid content yield is ≥90%.