CN1039705A - Remove caffeine in the coffee with caffeic acid - Google Patents

Remove caffeine in the coffee with caffeic acid Download PDF

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Publication number
CN1039705A
CN1039705A CN 88104741 CN88104741A CN1039705A CN 1039705 A CN1039705 A CN 1039705A CN 88104741 CN88104741 CN 88104741 CN 88104741 A CN88104741 A CN 88104741A CN 1039705 A CN1039705 A CN 1039705A
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China
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caffeine
caffeic acid
coffee
extract
solution
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CN 88104741
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Chinese (zh)
Inventor
威廉·沃尔特·卡利达
富阿德·扎奇·沙尔利
巴里·林·泽勒
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通用食品公司
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Priority to US06/870,197 priority Critical patent/US4767634A/en
Application filed by 通用食品公司 filed Critical 通用食品公司
Priority to CN 88104741 priority patent/CN1039705A/en
Publication of CN1039705A publication Critical patent/CN1039705A/en

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Abstract

A kind of method of removing caffeine is wherein having the coffee extract that will contain caffeine under the situation of water to contact with caffeic acid, and caffeine and caffeic acid form insoluble caffeine/caffeic acid complex, and this complex can separate from coffee extract.

Description

The present invention relates to remove the method for caffeine, this method is included in the extract that will contain caffeine under the situation of water and contacts with each other with caffeic acid, form caffeine and caffeinic insoluble complex, from the caffeine extract, separate caffeine/caffeic acid complex then.The extract that contains caffeine comprises and is used to remove coffee thereby directly contacts any solvent solution fresh or baked coffee, can be the aqueous solution or non-aqueous solution; And comprise any solvent solution afterwards that contacts with each other with the solvent solution that once was used for decaffeination, can be the aqueous solution or non-aqueous solution.
Many numerous being born in the art of technology of removing caffeine.A kind of widely used method be Beriy etc. at United States Patent (USP) 2,309, the water that is referred to as usually that discloses in No. 092 is removed the caffeine technology.Remove in the method for caffeine at water, the fresh coffee beans of hydration extract in multi-stage countercurrent extractor group with the fresh coffee extract that contains caffeine less.Fresh coffee extract along with enter and by the extractor group and with contact by the coffee bean of removing caffeine with subtracting in, it becomes more and more is rich in caffeine.The coffee extract that is full of caffeine of being discharged by extractor group afterbody from wherein removing caffeine, and then turns back to extraction system through handling.Caffeine is removed by contacting with each other with organic solvent from the fresh coffee extract, and such organic solvent generally is with halogenated organic solvent such as carrene.When the technology that water is removed caffeine is used widely, in food processing, avoid with an organic solvent more and more becoming desired.
Also has the other caffeine technology of removing, but shortcoming is arranged unavoidably all, for example: the European patent 0 that is awarded in May 19 nineteen eighty-two, 008, attached dose of sugar agent carbon alive is carried in the use that discloses in No. 398, though this method has been avoided with an organic solvent, activated carbon adsorbent often causes the coffee DDGS that also adsorbs a non-caffeine except the absorption caffeine, has so seriously damaged the economy of this method.
Husiani etc. are at United States Patent (USP) 4,315, have disclosed about removing the integrated approach of caffeine in the moisture bitter edible plant extract in No. 036.The cooling of moisture bitter edible plant extract is made it to be settled out the caffeine that has been present in the bitter edible plant and the insoluble complex of cold water of tannin.This method is convenient to utilize and has been present in the complexant in the bitter edible plant and does not need other interpolation.Though tannin/caffeine complex has good insoluble and therefore can be precipitated out, tannin like this is not present in the moisture coffee extract.
Chemical compound lot as the natural compound that contains in some coffees, is that known and caffeine form complex.For example: I.Horman and R.Viani are at J.Food Sci, 37(1972) discerned 10 kinds of such caffeine complexs in " character and the conformation of caffeine in the coffee-chlorogenic acid salt complex " literary composition of delivering in the 925-927 page or leaf, and comprise the existing fully water soluble coffee tannic acid/caffeine complex of research.Though infer that earlier this complexant promptly can be used for removing the method for caffeine so if can form water-fast caffeine complex, also do not differentiate the natural compound that contains in these coffees up to now.In addition, the relative strong chlorogenic acid/caffeine complex that splits will be competed and/or divide to the natural complexant of any this class all mutually with chlorogenic acid.
The invention relates to a kind of method of removing caffeine, this method is included in water and exists down, contact with each other with the coffee extract that contains caffeine with caffeic acid, wherein this caffeine and this caffeic acid form insoluble caffeine/caffeic acid complex, separate this caffeine/caffeic acid complex then from this coffee extract.This definition that contains coffee extract is included as any solvent solution of the coffee of removing coffee thereby directly contacting fresh or roasting, can be the aqueous solution or non-aqueous solution, and comprise with being used in the contacted any solvent solution afterwards of the solvent solution of removing caffeine, can be the aqueous solution or non-aqueous solution.
Found when application is of the present invention, can uses a kind of method that coffee is removed caffeine, but coffee is had only very little adverse effect.
Caffeic acid is the yellow crystal thing, begins to soften in the time of about 195 ℃, and when being lower than about 25 ℃, it is slightly soluble in water, but when being higher than about 80 ℃, it is infinitely water-soluble, infinitely is fused to alcohol in extremely wide temperature range.Yet we are surprised to find that in wide temperature range caffeic acid/caffeine complex is insoluble to solution.Though reported once that the content of caffeic acid in roasting and ground coffee was by weight up to 0.5%, but have now found that in fact that caffeic acid only is present in the fresh coffee on a small quantity and more relatively but be present in slightly in the coffee of roasting, in the coffee powder of the coffee bean of roasting or typical solubility, only contain have an appointment ten thousand/several.The relatively large acid that produces from caffeic acid in roasting coffee is one of abundanter caffeine tannic acid roasting catabolite of content.Being used for caffeic acid of the present invention can chemical synthesis, but preferably obtains from roasting coffee, or obtains by the acid hydrolysis effect of caffeine tannic acid, so that produce the effect of removing caffeine together with the native compound in the coffee.
Caffeic acid and special applicability is arranged, because it forms insoluble complex in coffee extract effect is not subjected to exist in this extract the influence of a large amount of caffeine tannic acid, be not subjected to the association constant of caffeic acid/caffeine complex to be lower than the influence of the association constant of caffeine tannic acid/caffeine complex yet.Horman etc. report that in the above-mentioned paper of mentioning the association constant of caffeine tannic acid/caffeine complex is 16.9, and the association constant of caffeic acid/caffeine complex is 12.2.Because association constant is measuring of complex relative intensity, be to add caffeic acid can disconnect caffeine tannic acid/caffeine complex of determining to be present in the coffee extract unexpectedly, forming insoluble colloidal state caffeic acid/caffeine complex then, is expectability such result not based on the association constant of having reported.
According to the present invention,, in the presence of water, caffeic acid and the extract that contains caffeine are merged in order from contain the caffeine extract, to remove caffeine.This contains the caffeine extract can be any solvent solution for removing coffee thereby directly contacting with the coffee of fresh or roasting, comprises the aqueous solution or non-aqueous solution; This contains the caffeine extract can also be with the solvent solution afterwards that the caffeine extract contacts with each other that contains that obtains from the coffee of fresh or roasting, can be the aqueous solution or non-aqueous solution.
Zeller etc. are at United States Patent (USP) 4,521, the embodiment that the coffee extract of narrating in 438 is removed the caffeine method has narrated a method, the caffeine extract that contains wherein is to obtain by the coffee extract that contacts fresh or roasting, be used for removing caffeine from coffee, this embodiment draws in this article and is reference.
The fresh coffee extract generally contains 20%-35% coffee DDGS and 0.5%-1.0 caffeine by weight by weight.The roasting coffee extract that is generally used for preparing soluble coffee also can be removed caffeine.This class roasting coffee extract often contains 10%-30% coffee DDGS and 0.5%-5% caffeine by weight by weight.This patent has been narrated and has been contained the caffeine extract and contact with caffeic acid, form insoluble colloidal state caffeic acid/caffeine complex, this insoluble complex is grown to serve as crystal gradually and can separates from liquid, then separatin non-soluble caffeic acid/caffeine crystal from remove caffeine liquid.Be preferably in about 50 ° of-125 ℃ of temperature caffeic acid and the coffee extract that contains caffeine are merged, the mol ratio of caffeic acid and caffeine was not less than 1: 1 usually, or was not higher than 3: 1, was preferably about 1.5: 1.In order to help crystal growth, this method comprises that also the amalgamation liquid with caffeic acid and caffeine extract is cooled to about 0 °-50 ℃.Can adding acid in coffee extract, that pH is reduced to is about 4.5, and this also helps crystal growth.This crystal complex can separate from coffee extract with resembling filtration or this class technology of centrifugation.
In another embodiment of the invention, containing the caffeine extract can contact to remove caffeine with fresh or roasting coffee with moistening carbon dioxide above-critical state or liquid phase.The method that contacts with each other with fresh coffee about the above-critical state carbon dioxide by Zosel at United States Patent (USP) 4,260, done more comprehensive narration in 369, draw at this paper and be reference.In this patent, coffee is 40-80 ℃ the atmospheric pressure limit of temperature range, 120-180 with the contact of moistening carbon dioxide and carries out in 5-30 hour.Coffee contacts in pressure vessel with moistening above-critical state carbon dioxide, and moistening above-critical state carbon dioxide enters pressure vessel, passes coffee and discharges then, wherein removes caffeine before moistening carbon dioxide comes back to pressure vessel earlier.According to the present invention, can from moistening above-critical state carbon dioxide, remove caffeine by in the moistening carbon dioxide solution of from the coffee contacting container, discharging, adding caffeic acid, grow into crystallization, separate from liquid by preamble is described then, return coffee contact container handling so removed the moistening above-critical state dioxide surface of caffeine.
Another embodiment of the present invention is that the fresh coffee beans can be removed caffeine with the ester solution of polyhydric alcohol and food carboxylic acid, this method by Mitchell etc. at United States Patent (USP) 3,682, done further narration in 648, draw at this paper and be reference.Aforesaid caffeine can be by in the presence of water, the extract that will contain caffeine contacts with caffeic acid, grows into crystallization gradually again and from wherein removing, then fractional crystallization from solution, basically caffeine-free coffee extract contacts with coffee more again, is used to remove caffeine.
Except that being used for above-mentioned containing the caffeine extract, this caffeic acid also can be used for once containing the caffeine extractant with any other fresh or that roasting coffee contacts with each other, comprises that water quality solvent or nonaqueous solvents carry out decaffeination.If when using non-aqueous solution, must have water so so that the formation of complex, if when this solvent and water immiscible, water is that the shape with free moisture exists; If or this solvent and water is can be miscible the time, water can dissolve in the solvent.
In another embodiment of the present invention, contact the caffeine in the extractant of being contained in that obtains by extraction solution with fresh or roasting coffee, can transfer in second or the extraction solution followed the preceding extract and remove caffeine, and caffeine is removed in containing in the caffeine extract of must obtaining from behind.
Saleeb etc. are at United States Patent (USP) 4,547, have narrated one embodiment of the invention in 378.According to this method, moisture roasting coffee extract is got liquid removes caffeine and carries out through the following steps, being about to the roasting coffee extract contacts with a kind of halogenated hydrocarbons such as carrene, so that the non-caffeine DDGS that makes caffeine and less amount goes from the roasting coffee extract is transferred to the solvent of caffeine, removing the roasting coffee extract of caffeine substantially can separate with the solvent that contains caffeine, then this caffeine solvent is concentrated into and is at least 4% concentration by weight, then the solvent that concentrates is contacted with suspension in the caffeinic water, this suspension contains the caffeic acid with caffeine equal molar quantities in solvent at least.When caffeic acid-caffeine complex after aqueous phase forms, leach crystallization, water phase separated from caffeine solvent still contains non-caffeine DDGS in this caffeine solvent then, so it is added in the roasting coffee extract of removing caffeine substantially again.The caffeine organic solvent is removed from roasting coffee, then with this roasting coffee extract drying, forms the soluble coffee that tool improves fragrance.
Other embodiments of the present invention be to use afterwards contain the caffeine extract, this method is similar to above-mentioned above-critical state carbon dioxide method.Yet, caffeic acid and different moistening above-critical state carbon dioxide contact of discharging from the coffee contacting container, be that moistening carbon dioxide at first contacts in scrubbing tower with other solvent (for example water) on the contrary, wherein water is to be used for removing caffeine from moistening above-critical state carbon dioxide.Promptly contact with caffeic acid after coming out from water wash column, and grow into the insoluble crystal of caffeic acid and caffeine complex there, can remove as stated above, this water of removing caffeine is recycled in the scrubbing tower then.When passing through water along with very a small amount of coffee aroma material precursor, some coffee aroma material precursors finally can make water saturated, and these water are circulated to scrubbing tower, thereby have only a small amount of coffee aroma material precursor by losing in this system.
The embodiment that the present invention also has is that the water extract that contains caffeine can pass through it with contacting with the immiscible fatty material of water, to remove caffeine from extract.For example Pagliaro etc. is at United States Patent (USP) 4,465, the method for narration in 699, and according to this method, the caffeine extract can be from wherein removing caffeine with the contact of water-immiscible liquid fat material.This fat material comprises saturated and undersaturated fat and oils, as caffeol.The fat material should be kept time enough with extract contact and caffeine can be transferred to the fatty material from this extract go, the fatty material that will be full of caffeine then separates with aqueous extract, again suspension in the caffeinic water is contacted with this fat material, caffeine is just transferred to aqueous phase, when caffeine enters water, it and caffeic acid form insoluble crystallization complex, and are precipitated out from solution at once.When after this individual system is removed caffeine, there is more caffeine to transfer to water, rebulid partition equilibrium, this operation proceeds to fatty material always and reaches desired and remove till the caffeine degree.Therefore, after oil was removed caffeine, water had been removed caffeine too.The valuable coffee component that contains in the water can instead be added in the extract flow and again with new caffeol contact, and is last, and water will become by non-caffeine compound institute saturated, and this is to wish the phase to reach.Water is to have removed on the one hand caffeine, in addition the aspect by non-caffeine solids bag and, so it can not stop any follow-up caffeine to shift, but it can suppress non-caffeine solids and shifts.Because fatty material is that so circulation is more than, thereby it will become by non-caffeine compound institute saturated at last.
The last embodiment of the present invention is except that using fatty material, the caffeine solvent of non-halo also can be used in into the coffee extract of removing caffeine as ethyl acetate; Benzylalcohol; Hydro carbons such as dimethylbenzene or non-aromatic hydrocarbon such as liquid cycloalkane; Ether; Hydro carbons comprises aromatic hydrocarbon such as dimethylbenzene or non-aromatic hydrocarbon such as low-molecular-weight liquid alcohol; And acetone.Strobel etc. are at United States Patent (USP) 4,256, have narrated above-mentioned these methods after in 774.In the method, being used to coffee to remove the coffee extract liquid of caffeine can be with being contacted by water saturated solvent such as ethyl acetate, caffeine is transferred in the solvent to be gone, the caffeic acid of drying is added in this solvent, form insoluble caffeine/caffeic acid complex there, can from solvent, separate.Do not have water layer in this method, yet water is dissolved in the ethyl acetate.
The following example is to further specify of the present invention, but it must be understood that the present invention is not limited to being described in detail of this paper.
Embodiment 1
With 30.0g water, 1.65g caffeine tannic acid and 0.9g caffeine merge the aqueous solution that is prepared into equimolar caffeine tannic acid and caffeine, and solution is heated near boiling, will weigh the equimolar a caffeic acid adding of 0.85g and be dissolved in this hot solution.Solution is cooled to environment temperature, observes crystalline growth after about 1 hour, after 12-14 hour, leaches crystallization with coarse filter paper from solution.Then remove about 93% caffeine by the analysis showed that, the caffeine tannic acid of removing simultaneously is less to measuring its amount.
Analysis for caffeine in this example and following example is undertaken by high efficiency liquid chromatography, and measures the degree of removing caffeine by the variation of caffeine characteristic peak area.Use Resolve chromatographic column (the spherical C of 5 μ 18; 3.9mm * 15cm) measure at the about 280nm of wavelength for caffeine and caffeic acid, flow by 0.0033 MKH PO, methyl alcohol and acetate are formed with 80: 20: 4 parts ratio respectively.Analysis is carried out in room temperature, adopts isocratic elution, simultaneously with the flow of 1.5ml/min and the sample of injection 5ml.Before analyzing with solution with mobile phase dilution to total solids be 0.1%(by weight).
Example 2
The 0.9g caffeic acid being dissolved in 90.0g being prepared into the aqueous solution, then 10.0gg is contained 9.5%(by weight near the water of boiling) coffee extract crossed of the constant pressure and dry of caffeine is dissolved in this solution.10.0g coffee is dissolved in the 90.0g water prepares control sample.Make above-mentioned two kinds of coffee solution cooling, after 12-14 hour, in containing caffeinic solution, observe crystallization, and control sample is not observed crystallization.Observe the crystallization of further growth after one week in containing caffeic acid solution, decant supernatant liquor from crystal solution, this solution is placed a week again, the caffeine of finding after the liquor analysis that takes a morsel to contain is than originally lacking 30%.Do not observe crystallization in the control sample.After second week, observe crystalline growth once more in containing caffeinic solution, slowly pour out supernatant liquor from crystal solution, this solution that takes a morsel is analyzed and is found to contain caffeine than originally lacking 65%, analyze this crystallization, find that it is pure basically 1: 1 mole of caffeic acid/caffeine complex; Control sample is not observed crystallization, the analysis found that initial caffeine also all exists.
Example 3
By containing 8.7%(by weight) coffee extract of the constant pressure and dry of caffeine prepares 10%(by weight) coffee solution, solution is divided into 4 parts, be heated to 70 ℃ then, press caffeic acid to the mol ratio of coffee because of 1.1: 1, caffeic acid is added wherein in three sample solutions, then 4 sample solutions are cooled to 40 ℃, contain caffeinic sample to two and add acetate, make the pH of first sample reduce to 4.5, second pH reduces to 4.2,4 samples stir and regularly sample secondary at 40 ℃, the results are shown in down in the tabulation.
Table
% removes caffeine
Sample acetate pH 24 hours 5 days
1.(contrast-no caffeic acid) do not have 5.1
2. do not have 4.9 9 54
3. have 4.5 49 64
4. have 4.2 64 70
After 5 days, 2-4 handles with ultracentrifugation with sample, 350,000 times of gravity centrifugal treating 30 minutes, leaches crystalline solid, analyzes crystalline solid and finds that it is pure basically 1: 1 mole of caffeic acid/caffeine complex, does not observe crystallization in control sample 1.
Example 4
1. contain 0.6% caffeine (by weight) and contain the about 15%(of total solid by weight) the roasting coffee extract be to obtain by multi-stage countercurrent extractor group with 6 grades, about 180 ℃ of supply water temperature.
2. roasting coffee extract is concentrated into about 55% solids (by weight) concentration in the Centritherm evaporimeter, from wherein removing fragrance and fragrance matter.
3. be diluted to about 25% total solid matters (by weight) concentration and 1% caffeine (by weight) through the 2 roasting coffee extract of handling.
4. under room temperature condition, in KArr extracting post the roasting coffee extract is contacted with carrene, the weight ratio of carrene and roasting coffee extract is 4.5: 1, and the degree of removing caffeine is for surpassing former 97% of the caffeine weight that exists.The carrene of from Karr extracting post, emitting.Contain about 0.25% total soluble solid.Caffeine concentration be 0.17%(by weight), this residue in 0.25% is non-caffeine DDGS.
5. in distillation still, dichloromethane solution is concentrated into total solids 10.5%(by weight) and 7.0% caffeine (by weight).
6. suspension contacts in the caffeinic 500cc coffee of the 23g sour water with containing with 250cc carrene sample in beaker.Contact is about 30 minutes under the stirring of room temperature and mitigation, observes crystalline growth at the interface at water and carrene.
7. leach crystallization with coarse filter paper from liquid, place and make carrene and water layering, decant divides water outlet.Analyze this crystallization and find that it is the complex of equimolar caffeic acid and caffeine; Find that the existing caffeine that accounts for former existence 90% weight is removed after analyzing this carrene.
8. reclaim above-mentioned water and, be recovered to some non-caffeine DDGSs with the fresh washed with dichloromethane twice of 50cc.This washed with dichloromethane step be handle for the water that is applied to this aqueous suspension the third and be the replacement scheme of adding.
9. the carrene with twice 50cc merges from the above-mentioned solvent that obtains together, and this solvent is atmospherically distilled to the 110cc volume at 32 ℃-35 ℃.
10. in beaker, the 110cc carrene sample that concentrates is contacted with containing the caffeinic 110cc caffeic acid of 5g water slurry.The water that is obtained by the 8th step is got a part and is used to prepare water slurry.Under the stirring of room temperature and mitigation, contact about 30 minutes again, observe crystalline growth at the interface once more at water and carrene.
11. 7 separate said components once more set by step, find to have removed again other 70% caffeine (by weight) that is present in the carrene.The caffeine total amount of removing through two steps reach initial existence caffeine about 97%(by weight).
12. the carrene of step 11 is added to the roasting coffee extract of the decaffeination of step 4, in about 65 ℃ and the about 0.5 atmospheric pressure vacuum distillation of absolute pressure, therefrom removes carrene then.
13. the water with step 8 and 11 adds in the extract of step 12 then, and extract is diluted to common trial test concentration, is approximately total solid matters 1%(by weight).
14. under above-mentioned the same terms, preparation is removed the control sample of the roasting coffee extract of caffeine with carrene, but carrene is herein no longer removed caffeine, also no longer returns to be added in the technical process.Control sample also is diluted to and contains total solid weight about 1%.
Taste evaluation 15. give the expert by 13 extracts that obtain of step and control sample, through judging, think the stronger senses of taste of extract tool in 13 steps, control sample is then thin significantly.
Example 5
Ethyl acetate with 21 contacts with 75cc water, and experience 1 hour and make its equilibrium establishment, what make about 66cc water-solublely goes into ethyl acetate, removes remaining water layer, add the 35g caffeine to this in by water saturated ethyl acetate, place and leach insoluble caffeine after 18 hours.Approximately dissolve the 25g caffeine, obtained containing the solution (by weight) of 1.3% caffeine.
Then the 2.52g caffeic acid is added to above-mentioned 250cc by in the saturated ethyl acetate of water and caffeine, become every mole of caffeine and contain 1.5 moles of caffeic acids.This suspension stirred 3 hours, can observe caffeine/caffeic acid crystallization during this period, and the caffeic acid that expression adds cooperates with caffeine, and with mixture standing sedimentation 1 hour, sample analysis caffeine, discovery is removed the caffeine degree and reached 67%.
Example 6
The vegetable oil of 500cc volume contacted and stirs 1 hour with 100cc water and 5g caffeine, then the insoluble caffeine of filtering and from aqueous phase separating plant oil.The water saturated vegetable oil of this usefulness is measured by analysis and is contained 0.11% caffeine (by weight) of having an appointment.The above-mentioned oil of 200cc volume is contacted with the 0.5g caffeic acid with 25cc, and mixture stirs and to make it equilibrium establishment in 18 hours, and the degree of caffeine is removed in assay determination from oil then, found that this oil removed 96% caffeine.From sample, leach solid, thereby the obvious change of examining under a microscope crystalline texture proves that the caffeic acid that is close to half changes into the caffeine complex.
Example 7
In extraction tower, the fresh coffee beans are contacted with the above-critical state carbon dioxide and remove caffeine.This above-critical state carbon dioxide washes with water and removes caffeine then, produces to contain 0.3%(weight) the caffeine aqueous solution, pH is 2.6.
The above-mentioned aqueous solution of 150g is placed beaker, and this sample contains the caffeine that 0.45g dissolves in, and adds 1.25g caffeic acid powder in this solution, so that caffeic acid reaches 3: 1 to the mol ratio of caffeine.Sample is heated to boiling on agitator disk, dissolves in caffeic acid again, make solution be cooled to room temperature, produce the also crystallization and precipitating of excessive caffeic acid simultaneously of caffeic acid complex crystal precipitation.
After one day, extract the supernatant liquor sample and analyze caffeine, find that removing the caffeine degree reaches 92% with high efficiency liquid chromatography.Utilize the pure water solution that contains 0.3% caffeine also to prepare control sample under the same conditions.The result who obtains with same procedure is that to remove the caffeine degree be 93%, and this caffeine of function effect represent that non-caffeine solids removes to(for) this method is very little.

Claims (21)

1, a kind of method of removing caffeine, this method comprises:
(a) the coffee extract solution that will contain caffeine in the presence of water contacts with caffeic acid, wherein caffeine and caffeic acid form insoluble caffeine/caffeic acid complex and
(b) separate caffeine/caffeic acid complex from coffee extract solution.
2, be moistening above-critical state carbon dioxide by the process of claim 1 wherein that this contains the caffeine extract solution.
3, by the method for claim 2,, caffeic acid is contacted with moistening above-critical state carbon dioxide wherein about 50 ℃-Yue 125 ℃ of temperature ranges.
4, by the method for claim 2, wherein this to contain the caffeine extract be the fresh coffee extract.
5, by the method for claim 2, wherein this to contain the caffeine extract be the roasting coffee extract.
6, by the method for claim 2, wherein caffeic acid with the coffee extract solution that contains caffeine be caffeic acid to coffee because of mol ratio be at least under 1: 1 the condition and combine.
7, by the process of claim 1 wherein that this caffeine/caffeic acid complex is to separate with coffee extract solution by centrifugal action.
8, be a kind of aqueous solution by the process of claim 1 wherein that this contains the caffeine extract solution, the said aqueous solution contains the caffeine that obtains with the contact of moistening above-critical state two carbonitrides in front.
9, by the method for claim 8, wherein caffeic acid is to combine caffeic acid is at least 1: 1 condition to the mol ratio of caffeine under with containing the caffeine aqueous solution.
10, by the method for claim 8, wherein caffeic acid is to contact in the about 125 ℃ of temperature of about 50-with the aqueous solution.
11, by the process of claim 1 wherein that this contains the caffeine solvent that the caffeine extract solution is non-halo, this solvent contains the caffeine that obtains with containing the contact of caffeine extract solution in front.
12, by the method for claim 11, wherein the caffeine extract solution that contains of front is the fresh coffee extract.
13, by the method for claim 11, wherein the caffeine extract solution that contains of front is the roasting coffee extract.
14, by the method for claim 11, wherein the caffeine solvent in this non-fontanel generation is a kind of fatty material.
15, by the method for claim 14, should the fat material be a vegetable oil wherein.
16, by the method for claim 15, wherein this vegetable oil is a caffeol.
17, by the method for claim 11, wherein this non-halo caffeine solvent is to be selected to comprise aromatics and alcohol non-aromatics, ester, ether and hydro carbons.
18, by the method for claim 17, wherein this non-halo caffeine solvent is a kind of ester.
19, by the method for claim 18, ester wherein is an ethyl acetate.
20, by the method for claim 11, wherein caffeic acid is to combine caffeic acid is at least 1: 1 condition to the mol ratio of caffeine under with the non-halo extract solution that contains caffeine.
21, by the method for claim 11, wherein caffeic acid with the non-halo extract that contains caffeine be or be lower than this caffeine solvent boiling temperature and combine.
CN 88104741 1986-06-03 1988-07-29 Remove caffeine in the coffee with caffeic acid CN1039705A (en)

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US06/870,197 US4767634A (en) 1986-06-03 1986-06-03 Coffee decaffeination with caffeic acid
CN 88104741 CN1039705A (en) 1986-06-03 1988-07-29 Remove caffeine in the coffee with caffeic acid

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