CN115894236A - Preparation method of caffeine-free chlorogenic acid - Google Patents
Preparation method of caffeine-free chlorogenic acid Download PDFInfo
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- CN115894236A CN115894236A CN202211561391.5A CN202211561391A CN115894236A CN 115894236 A CN115894236 A CN 115894236A CN 202211561391 A CN202211561391 A CN 202211561391A CN 115894236 A CN115894236 A CN 115894236A
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- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 title claims abstract description 45
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 title claims abstract description 45
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 title claims abstract description 45
- 235000001368 chlorogenic acid Nutrition 0.000 title claims abstract description 45
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 title claims abstract description 45
- 229940074393 chlorogenic acid Drugs 0.000 title claims abstract description 45
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 title claims abstract description 45
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 100
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000002245 particle Substances 0.000 claims abstract description 67
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229960001948 caffeine Drugs 0.000 claims abstract description 50
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 claims abstract description 50
- 241000533293 Sesbania emerus Species 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- LOHGGLZYTJNUAL-UHFFFAOYSA-M sodium;ethanol;chloride Chemical class [Na+].[Cl-].CCO LOHGGLZYTJNUAL-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 238000010828 elution Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 63
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- 238000009210 therapy by ultrasound Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 21
- 238000004108 freeze drying Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 12
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- 239000000084 colloidal system Substances 0.000 claims description 11
- 239000003480 eluent Substances 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 7
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- 238000010299 mechanically pulverizing process Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 13
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- 239000010419 fine particle Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- ZSOMPVKQDGLTOT-UHFFFAOYSA-J sodium green Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.COC=1C=C(NC(=O)C=2C=C(C(=CC=2)C2=C3C=C(Cl)C(=O)C=C3OC3=CC([O-])=C(Cl)C=C32)C([O-])=O)C(OC)=CC=1N(CCOCC1)CCOCCOCCN1C(C(=C1)OC)=CC(OC)=C1NC(=O)C1=CC=C(C2=C3C=C(Cl)C(=O)C=C3OC3=CC([O-])=C(Cl)C=C32)C(C([O-])=O)=C1 ZSOMPVKQDGLTOT-UHFFFAOYSA-J 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 2
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 2
- AAWZDTNXLSGCEK-LNVDRNJUSA-N (3r,5r)-1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid Chemical compound O[C@@H]1CC(O)(C(O)=O)C[C@@H](O)C1O AAWZDTNXLSGCEK-LNVDRNJUSA-N 0.000 description 1
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 1
- 241000205585 Aquilegia canadensis Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 241000227999 Coffea canephora Species 0.000 description 1
- 235000002187 Coffea robusta Nutrition 0.000 description 1
- AAWZDTNXLSGCEK-UHFFFAOYSA-N Cordycepinsaeure Natural products OC1CC(O)(C(O)=O)CC(O)C1O AAWZDTNXLSGCEK-UHFFFAOYSA-N 0.000 description 1
- 241000208689 Eucommia ulmoides Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- AAWZDTNXLSGCEK-ZHQZDSKASA-N Quinic acid Natural products O[C@H]1CC(O)(C(O)=O)C[C@H](O)C1O AAWZDTNXLSGCEK-ZHQZDSKASA-N 0.000 description 1
- 241001107098 Rubiaceae Species 0.000 description 1
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- 229940074360 caffeic acid Drugs 0.000 description 1
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- 235000019693 cherries Nutrition 0.000 description 1
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of extraction of chlorogenic acid, and particularly relates to a preparation method of caffeine-free chlorogenic acid, which comprises the following steps: the method comprises the steps of crushing green coffee beans into particles, performing sodium chloride-ethanol salt-alcohol composite extraction, performing acetone extraction by using acetone, and performing resin elution and solvent dissolution to obtain caffeine-free chlorogenic acid and achieve the effect of co-production of caffeine. The invention solves the problem that the chlorogenic acid contains caffeine, realizes the gradient removal of the caffeine by adopting a mode of combining resin adsorption and a solvent, and realizes the leaching effect of the caffeine by matching with the poor dissolution of the chlorogenic acid and the caffeine.
Description
Technical Field
The invention belongs to the technical field of extraction of chlorogenic acid, and particularly relates to a preparation method of caffeine-free chlorogenic acid.
Background
Chlorogenic acid is an ester formed by caffeic acid and quinic acid, is an important bioactive substance, has wide pharmacological action and biological activity, is not only a main effective component of numerous medicinal materials and Chinese patent medicines for resisting bacteria, removing toxicity, diminishing inflammation and benefiting gallbladder, but also has three unstable parts of ester bonds, unsaturated double bonds and polyphenol in the molecular structure, and has the effects of resisting viruses, increasing leucocytes, resisting tumors, reducing blood pressure, reducing blood fat, eliminating free radicals, exciting central nervous systems and the like. Chlorogenic acid is widely present in plants, the content of honeysuckle, eucommia ulmoides and green coffee beans is high, and efficient extraction of chlorogenic acid from natural plants is a research hotspot at home and abroad. The green coffee bean is derived from seed of coffee cherries, coffea canephora and coffea maxima of Rubiaceae. The green coffee beans contain a large amount of chlorogenic acid, and can be used as a raw material of a chlorogenic acid extract. However, since caffeine is contained in the chlorogenic acid, it is difficult to remove caffeine mixed in the chlorogenic acid extract as impurities during extraction of the chlorogenic acid, resulting in poor purity of the chlorogenic acid.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of caffeine-free chlorogenic acid, which solves the problem that the chlorogenic acid contains caffeine, realizes gradient removal of the caffeine by adopting a mode of combining resin adsorption and a solvent, and realizes the leaching effect of the caffeine by matching poor dissolution of the chlorogenic acid and the caffeine.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of caffeine-free chlorogenic acid comprises the following steps:
step 1, grinding green coffee beans into particles, adding the particles into sodium chloride-ethanol glue solution, uniformly stirring, and performing wet ball milling treatment to form homogeneous colloid; the green coffee beans are mechanically crushed to form fine powder particles, the mass ratio of sodium chloride to ethanol in the sodium chloride-ethanol glue solution is 1-2, the mass ratio of the green coffee beans to the sodium chloride is 10-1-3, and the stirring speed is 1000-2000r/min; the temperature of the wet ball milling treatment is 30-50 ℃, and the ball milling pressure is 0.5-0.9MPa; in the processing process, the green coffee beans are mechanically crushed to form fine powder particles, the particles belong to physical mechanical damage and cannot influence active ingredients, and meanwhile, in the crushing process, the coffee beans are broken under stress, so that the exposed area is greatly increased, and the subsequent contact area is increased sharply; when the fine powder particles are placed in a sodium chloride ethanol glue solution, sodium chloride is insoluble in ethanol, fine particles with a colloid structure are formed in the ethanol, namely, the sodium chloride forms a stable dispersion structure in the system, and meanwhile, the sodium chloride is uniformly distributed in the ethanol in a state of the fine particles, and when the fine green coffee particles are placed in the glue solution, the fine sodium chloride particles can be further crushed as ball-milled particles on the fine powder particles based on the stability of the fine sodium chloride structure in the ball milling process, so that the particle size of the fine particles is further reduced, the specific surface area of the green coffee particles is increased, meanwhile, the water absorption of the sodium chloride can absorb and release water molecules on the surfaces of the green coffee particles in the contact process, and the inactivated state of the surfaces of the green coffee particles is caused, namely, the activity of the green coffee particles is reduced, the grindability of the green coffee particles is improved, the refining effect of the green coffee particles is greatly improved, and the fine green coffee particles are formed into a primary dissolution system based on the permeability and dissolution effect of the ethanol; therefore, in the step, the primary dissolution is a composite extraction system formed by salt extraction and alcohol extraction;
step 2, standing and airing the homogeneous colloid, adding acetone for low-temperature ultrasonic treatment for 20-30min, sealing for 2-3h, naturally cooling to obtain slurry, wherein the standing temperature is 30-40 ℃, the ultrasonic treatment concentration is 30-50g/L, the low-temperature ultrasonic treatment temperature is 5-10 ℃, the ultrasonic frequency is 50-70kHz, the sealing temperature is 55-60 ℃, and the initial pressure is 80-90% of atmospheric pressure, the step utilizes the volatility of ethanol, a semi-dry state is formed in the airing process, after the solvent is removed, the extract and particles after composite extraction are directly deposited in the semi-dry system, when the acetone is added, acetone dissolved substances in the extract can be rapidly dissolved to form a dissolved solution and uniformly dispersed in the ultrasonic process, sodium chloride and green coffee fine powder particles are uniformly distributed in the acetone to form a homogenized structure, based on the water absorption of the homogenized structure and the water absorption of the acetone, the water absorption of the acetone can further absorb water, the acetone is extracted, the permeation and converted into gas in the sealing and nursing process, the gas state is greatly matched to form a secondary dissolved water absorption effect, and the secondary leaching efficiency is improved;
step 3, standing the pulp at constant temperature to obtain concentrated solution and acetone solution, filtering the concentrated solution at constant temperature, washing with the acetone solution to obtain acetone dissolved filtrate, wherein the temperature of standing and concentrating at constant temperature is 30-40 ℃, the volume of the concentrated solution is 20-30% of the pulp, the temperature of filtering at constant temperature is 20-30 ℃, the acetone in the pulp is released by utilizing the high volatility of the acetone, the acetone solution and the concentrated acetone extract are obtained by cooling and collecting, sodium chloride and green coffee fine powder particles are removed simultaneously in the process of filtering at constant temperature, and the sodium chloride and green coffee fine powder particles are washed by utilizing the acetone solution obtained by concentrating;
step 4, concentrating the acetone dissolving filtrate to dryness, adding distilled water, and adjusting the pH to 6-6.5 to obtain acid liquor; then directly filling the acid liquor into XAD-16 macroporous resin for adsorption treatment to obtain a loss liquid, and eluting the macroporous resin to obtain caffeine eluent; the concentration temperature is 40-50 ℃, and acetone is recovered; the concentration of the added distilled water is 200-400g/L, the pH is adjusted by hydrochloric acid, the mass ratio of the resin to the acid solution is 1; the step of concentrating the acetone dissolving filtrate to dryness, recovering acetone, and using the acetone for the step 2, wherein the dissolving liquid can be converted into a water solvent from an acetone solvent by adding distilled water, the pH value is adjusted to acidity by using hydrochloric acid, and then the water solvent is placed into XAD-16 macroporous resin for adsorption treatment, caffeine in acid liquid is removed, the caffeine proportion in the loss liquid is not more than 5%, and caffeine adsorbed by the XAD-16 macroporous resin is released by an elution mode, so that caffeine eluent is obtained;
step 5, freeze-drying the loss liquid to obtain frozen particles, then putting the frozen particles into ether for low-temperature ultrasonic treatment for 20-50min, and filtering to obtain fine powder particles and filtrate, wherein the freeze-drying temperature is-20 ℃; the mass ratio of the frozen particles to the diethyl ether is 1-8, the low-temperature ultrasonic treatment temperature is 5-10 ℃, the ultrasonic frequency is 50-70kHz, distilled water is removed by utilizing a freeze drying mode in the step, the drying purpose is achieved, and chlorogenic acid particles containing caffeine are obtained; the chlorogenic acid particles are put into ether, the insolubility of the ether to the chlorogenic acid and the solubility of the ether to the caffeine are utilized, the caffeine in the whole system can be completely removed, meanwhile, the frozen particles can be heated in a low-temperature ultrasonic mode to form a certain dissolved substance to be released, the particles are opened in high-frequency oscillation, the caffeine in the particles is released and dissolved in the ether to achieve an excellent caffeine removing effect, and the chlorogenic acid particles without the caffeine are obtained after filtration; in the treatment process, the using amount of the diethyl ether is far larger than the mass of the frozen particles and far larger than the content of the caffeine, the caffeine can be completely dissolved by the diethyl ether based on the using amount of the diethyl ether, and the effect of completely releasing the caffeine is achieved by matching with vibration dispersion of ultrasonic treatment; the fine powder particles are chlorogenic acid.
Step 6, mixing the filtrate and the eluent to obtain a caffeine solution, concentrating for 2-4h, and freeze-drying to obtain a caffeine byproduct, wherein the concentration adopts reduced pressure distillation, the temperature of the reduced pressure distillation is 50-60 ℃, the pressure is 60-70% of the atmospheric pressure, and the temperature of the freeze-drying is-20 ℃; the method comprises the following steps of treating a caffeine solution in a concentration treatment mode, removing ethanol and ether, concentrating the whole solution, and converting the whole solution into a caffeine aqueous solution; the caffeine water solution is freeze-dried to realize the recycling of the caffeine.
As can be seen from the above description, the present invention has the following advantages:
1. the invention solves the problem that the chlorogenic acid contains caffeine, realizes the gradient removal of the caffeine by adopting a mode of combining resin adsorption and a solvent, and realizes the leaching effect of the caffeine by matching with the poor dissolution of the chlorogenic acid and the caffeine.
2. The invention utilizes sodium chloride as water absorption deactivator and grinding agent to form refinement and deactivation release of green coffee bean particles, achieves the effects of salt extraction and alcohol extraction, and realizes the primary extraction of coffee beans.
3. The invention uses acetone as solvent, forms acetone dissolution and osmotic dissolution under the mode of ultrasonic and sealing treatment, achieves the effect of secondary acetone dissolution, and simultaneously realizes the dissolution and separation of the extract by the secondary dissolution of the acetone to the former dissolution product.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A preparation method of caffeine-free chlorogenic acid comprises the following steps:
step 1, refining green coffee beans into particles, adding the particles into a sodium chloride-ethanol glue solution, uniformly stirring, and performing wet ball milling treatment to form a homogeneous colloid; the green coffee beans are mechanically crushed to form fine powder particles, the mass ratio of sodium chloride to ethanol in the sodium chloride-ethanol glue solution is 1; the temperature of the wet ball milling treatment is 30 ℃, and the ball milling pressure is 0.5MPa;
step 2, standing and airing the homogeneous colloid to be half-dry, then adding acetone for low-temperature ultrasonic treatment for 20min, sealing for 2h, and naturally cooling to obtain slurry, wherein the standing temperature is 30 ℃, the ultrasonic treatment concentration is 30g/L, the low-temperature ultrasonic treatment temperature is 5 ℃, the ultrasonic frequency is 50kHz, the sealing temperature is 55 ℃, and the initial pressure is 80% of the atmospheric pressure;
step 3, standing and concentrating the slurry at constant temperature to obtain a concentrated solution and an acetone solution, then filtering the concentrated solution at constant temperature, washing with the acetone solution to obtain an acetone dissolving filtrate, wherein the temperature of standing and concentrating at constant temperature is 30 ℃, the volume of the concentrated solution is 20% of the slurry, and the temperature of filtering at constant temperature is 20 ℃;
step 4, concentrating the acetone dissolving filtrate to dryness, adding distilled water, and adjusting the pH to 6 to obtain acid liquor; then directly filling the acid liquor into XAD-16 macroporous resin for adsorption treatment to obtain a run-off liquid, and eluting to obtain a caffeine eluent; the concentration temperature is 40 ℃, and acetone solution is recovered; the concentration of the added distilled water is 200g/L, the pH is adjusted by hydrochloric acid, the mass ratio of the resin to the acid solution is 1;
step 5, freeze-drying the loss liquid to obtain frozen particles, then putting the frozen particles into ether for low-temperature ultrasonic treatment for 20-50min, repeatedly washing the frozen particles for multiple times, and filtering the washed particles to obtain fine powder particles and filtrate, wherein the freeze-drying temperature is-20 ℃; the mass ratio of the frozen particles to the diethyl ether is 1;
and 6, mixing the filtrate and the eluent to obtain a caffeine solution, concentrating for 2 hours, and freeze-drying to obtain a caffeine byproduct, wherein the concentration adopts reduced pressure treatment, the temperature of the reduced pressure distillation is 50 ℃, the pressure is 70% of the atmospheric pressure, and the temperature of the freeze-drying is-20 ℃.
The product of this example was a pale green powder in which the purity of chlorogenic acid was 98.3%, caffeine content was not detected, and the product yield was 5.1%.
Example 2
A preparation method of caffeine-free chlorogenic acid comprises the following steps:
step 1, refining green coffee beans into particles, adding the particles into a sodium chloride-ethanol glue solution, uniformly stirring, and performing wet ball milling treatment to form a homogeneous colloid; the green coffee beans are mechanically crushed to form fine powder particles, the mass ratio of sodium chloride to ethanol in the sodium chloride-ethanol glue solution is 1; the temperature of the wet ball milling treatment is 50 ℃, and the ball milling pressure is 0.9MPa;
step 2, standing and airing the homogeneous colloid to be semi-dry, then adding acetone for low-temperature ultrasonic treatment for 30min, sealing for 3h, and naturally cooling to obtain slurry, wherein the standing temperature is 40 ℃, the ultrasonic treatment concentration is 50g/L, the low-temperature ultrasonic treatment temperature is 10 ℃, the ultrasonic frequency is 70kHz, the sealing temperature is 60 ℃, and the initial pressure is 90% of the atmospheric pressure;
step 3, standing and concentrating the slurry at a constant temperature to obtain a concentrated solution and an acetone solution, filtering the concentrated solution at a constant temperature, washing the concentrated solution by using the acetone solution to obtain an acetone dissolving filtrate, wherein the temperature of standing and concentrating at the constant temperature is 40 ℃, the volume of the concentrated solution is 30% of that of the slurry, and the temperature of filtering at the constant temperature is 30 ℃;
step 4, concentrating the acetone dissolving filtrate to dryness, adding distilled water, and adjusting the pH to 6.5 to obtain acid liquor; then directly filling the acid liquor into XAD-16 macroporous resin for adsorption treatment to obtain a run-off liquid, and eluting to obtain a caffeine eluent; the concentration temperature is 50 ℃, and acetone solution is recovered; the concentration of the added distilled water is 400g/L, the pH is adjusted by hydrochloric acid, the mass ratio of the resin to the acid solution is 1;
step 5, freeze-drying the loss liquid to obtain frozen particles, then putting the frozen particles into diethyl ether for low-temperature ultrasonic treatment for 50min, and filtering to obtain a filtrate of fine powder particles, wherein the freeze-drying temperature is-20 ℃; the mass ratio of the frozen particles to the diethyl ether is 1;
and 6, mixing the filtrate and the eluent to obtain a caffeine solution, concentrating for 4 hours, and freeze-drying to obtain a caffeine byproduct, wherein the concentration adopts reduced pressure distillation, the temperature of the reduced pressure distillation is 60 ℃, the pressure is 60% of atmospheric pressure, and the temperature of the freeze-drying is-20 ℃.
The product of this example was a pale green powder in which the purity of chlorogenic acid was 99.1%, caffeine components were not detected, and the product yield was 5.5%.
Example 3
A preparation method of caffeine-free chlorogenic acid comprises the following steps:
step 1, grinding green coffee beans into particles, adding the particles into sodium chloride-ethanol glue solution, uniformly stirring, and performing wet ball milling treatment to form homogeneous colloid; the green coffee beans are mechanically crushed to form fine powder particles, the mass ratio of sodium chloride to ethanol in the sodium chloride-ethanol glue solution is 1; the temperature of the wet ball milling treatment is 40 ℃, and the ball milling pressure is 0.7MPa;
step 2, standing and airing the homogeneous colloid to be half-dry, then adding acetone for low-temperature ultrasonic treatment for 25min, sealing for 3h, and naturally cooling to obtain slurry, wherein the standing temperature is 35 ℃, the ultrasonic treatment concentration is 40g/L, the low-temperature ultrasonic treatment temperature is 8 ℃, the ultrasonic frequency is 60kHz, the sealing temperature is 60 ℃, and the initial pressure is 85% of the atmospheric pressure;
step 3, standing and concentrating the slurry at a constant temperature to obtain a concentrated solution and an acetone solution, filtering the concentrated solution at a constant temperature, washing the concentrated solution by using the acetone solution to obtain an acetone dissolving filtrate, wherein the temperature of standing and concentrating at the constant temperature is 35 ℃, the volume of the concentrated solution is 25% of that of the slurry, and the temperature of filtering at the constant temperature is 25 ℃;
step 4, concentrating the acetone dissolving filtrate to dryness, adding distilled water, and adjusting the pH to 6.5 to obtain acid liquor; then directly filling the acid solution into XAD-16 macroporous resin for adsorption treatment to obtain a lost solution, and eluting to obtain a caffeine eluent; the concentration temperature is 45 ℃, and acetone solution is recovered; the concentration of the added distilled water is 300g/L, the pH is adjusted by hydrochloric acid, the mass ratio of the resin to the acid solution is 1;
step 5, freeze-drying the lost liquid to obtain frozen particles, then putting the frozen particles into diethyl ether for low-temperature ultrasonic treatment for 40min, and filtering to obtain filtrate of fine powder particles, wherein the freeze-drying temperature is-20 ℃; the mass ratio of the frozen particles to the diethyl ether is 1;
and 6, mixing the filtrate and the eluent to obtain a caffeine solution, concentrating for 3 hours, and freeze-drying to obtain a caffeine byproduct, wherein the concentration adopts reduced pressure treatment, the temperature of the reduced pressure distillation is 55 ℃, the pressure is 65% of the atmospheric pressure, and the temperature of the freeze-drying is-20 ℃.
The product of this example was a pale green powder in which the purity of chlorogenic acid was 98.7%, caffeine content was not detected, and the product yield was 5.3%.
It should be understood that the detailed description of the invention is only for illustrating the invention and is not limited to the technical solutions described in the embodiments of the invention. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; and are within the scope of the present invention as long as the requirements of use are met.
Claims (9)
1. A preparation method of caffeine-free chlorogenic acid is characterized by comprising the following steps: the method comprises the following steps:
step 1, grinding green coffee beans into particles, adding the particles into sodium chloride-ethanol glue solution, uniformly stirring, and performing wet ball milling treatment to form homogeneous colloid; mechanically pulverizing the green coffee beans to form fine powder particles;
step 2, standing and airing the homogeneous colloid to be half-dry, then adding acetone for low-temperature ultrasonic treatment for 20-30min, sealing for 2-3h, and naturally cooling to obtain slurry;
step 3, standing and concentrating the slurry at constant temperature to obtain a concentrated solution and an acetone solution, filtering the concentrated solution at constant temperature, and washing with the acetone solution to obtain an acetone dissolving filtrate;
step 4, concentrating the acetone dissolving filtrate to dryness, adding distilled water, and adjusting the pH to 6-6.5 to obtain acid liquor; then directly filling the acid liquor into XAD-16 macroporous resin for adsorption treatment to obtain a run-off liquid, and eluting to obtain a caffeine eluent;
step 5, freeze-drying the lost liquid to obtain frozen particles, then putting the frozen particles into ether for low-temperature ultrasonic treatment for 20-50min, and filtering to obtain fine powder particles and filtrate, wherein the fine powder particles are chlorogenic acid;
and 6, mixing the filtrate and the eluent to obtain a caffeine solution, concentrating for 2-4h, and freeze-drying to obtain a caffeine byproduct.
2. The method of preparing caffeine-free chlorogenic acid according to claim 1, characterized in that: the mass ratio of the sodium chloride to the ethanol in the sodium chloride-ethanol glue solution in the step 1 is 1-2, the mass ratio of the green coffee beans to the sodium chloride is 10-1-3, and the stirring speed is 1000-2000r/min; the temperature of the wet ball milling treatment is 30-50 ℃, and the ball milling pressure is 0.5-0.9MPa.
3. The method of preparing caffeine-free chlorogenic acid according to claim 1, characterized in that: the standing temperature in the step 2 is 30-40 ℃, the concentration of ultrasonic treatment is 30-50g/L, the temperature of low-temperature ultrasonic treatment is 5-10 ℃, the ultrasonic frequency is 50-70kHz, the temperature of sealing treatment is 55-60 ℃, and the initial pressure is 80-90% of the atmospheric pressure.
4. The method of preparing caffeine-free chlorogenic acid according to claim 1, characterized in that: the temperature of the constant-temperature standing concentration in the step 3 is 30-40 ℃, the volume of the concentrated solution is 20-30% of the slurry, and the temperature of the constant-temperature filtration is 20-30 ℃.
5. The method of preparing caffeine-free chlorogenic acid according to claim 1, characterized in that: the concentration temperature in the step 4 is 40-50 ℃, and acetone liquid is recovered; the concentration of the solution after the distilled water is added is 200-400g/L, and the pH is adjusted by hydrochloric acid.
6. The method of preparing caffeine-free chlorogenic acid according to claim 1, characterized in that: the mass ratio of the resin to the acid solution in the step 4 is 1-30, the ethanol aqueous solution is adopted for elution, the volume of ethanol in the ethanol aqueous solution accounts for 70-80%, and the ethanol aqueous solution adopted for elution is 5-10 times of the mass of the resin.
7. The method of preparing caffeine-free chlorogenic acid according to claim 1, characterized in that: the temperature of the freeze drying in the step 5 is-20 ℃; the mass ratio of the frozen particles to the diethyl ether is 1.
8. The method of preparing caffeine-free chlorogenic acid according to claim 1, characterized in that: the temperature of the low-temperature ultrasonic treatment in the step 5 is 5-10 ℃, and the ultrasonic frequency is 50-70kHz.
9. The method of preparing caffeine-free chlorogenic acid according to claim 1, characterized in that: the concentration treatment in the step 6 adopts reduced pressure treatment, the temperature of the reduced pressure distillation is 50-60 ℃, the pressure is 60-70% of the atmospheric pressure, and the temperature of the freeze drying is-20 ℃.
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