WO2015054907A1

WO2015054907A1 - Green coffee bean extract and production method thereof

Info

Publication number: WO2015054907A1
Application number: PCT/CN2013/085512
Authority: WO
Inventors: 卢庆国; 昝立峰; 田洪; 王立志; 胡晓梅; 孙国峰; 程远欣
Original assignee: 晨光生物科技集团股份有限公司
Priority date: 2013-10-18
Filing date: 2013-10-18
Publication date: 2015-04-23
Also published as: CN105899222B; CN105899222A

Abstract

Provided is a method for producing green coffee bean extract, the method comprising: conducting supercritical carbon dioxide treatment on green coffee bean raw material, and then employing organic solvent extraction to obtain the green coffee bean extractive. The obtained green coffee bean extractive product mainly contains 28-37% 5-caffeoylquinic acid, and 45-60% total chlorogenic acid. The present invention has no harmful residual solvent, dramatically reduces pesticide residue, and ensures no loss of content of effective ingredients while removing caffeine; the obtained green coffee bean extract product has high weight yield, high earnings, and low costs, greatly increases the content of effective ingredients, and is superior to the prior art, thus being suitable for large-scale industrial production and having broad application prospects and economic value.

Description

Green coffee bean extract and production method thereof

The present invention relates to the field of extracts and extraction techniques, and in particular to a green coffee bean extract, and a method of producing the same. Background technique

The green coffee bean extract is extracted from the seeds of the genus Coffea sp., and its main component is 5-CQA (5-caffeoylquinic acid) and its homologue 3-CQA (3). -caffeoylquinic acid), 4-CQA (4-caffeoylquinic acid), 3-FQA (3-propionylquinic acid), 4-FQA (4-propionylquinic acid) and 5-FQA (5 - feruloyl quinic acid), etc., these components belong to chlorogenic acid or its isomer.

Green coffee bean extract has pharmacological activities such as anti-oxidation, anti-virus, anti-cancer, antibacterial or cellulite. According to the latest research by American scientists, the green coffee bean extract has a good fat-reducing function, and a variety of health care products with green coffee bean extract as the main component have been pushed to the market.

The current mainstream process for producing green coffee bean extracts is to dilute the green coffee beans with dilute alcoholic products. The products produced by the related processes have residual solvents such as hexamethylene chloride and chloroform; and the market in the United States and the European Union requires a content of less than 1 ppm, and there is also a strict limit on the chloroform, and the above process is difficult to achieve. In India, Kulathoran Ramalakshmi et al. extracted powdered secondary coffee beans with methanol, and extracted the oil and fat in the coffee bean extract by reflux extraction, chloroform to remove caffeine, and ΗΡ-20 macroporous adsorption resin to purify the product. The weight yield was 7.46 ~ 10.46%, and the methanol extract was obtained by drying. The total chlorogenic acid content was between 28.70 and 30.50%.

Chinese patent application CN201310116237.1 (publication number: CN103232346A, publication date: August 7, 2013) discloses a production process for extracting chlorogenic acid from green coffee beans, which uses green coffee beans as raw materials, is crushed and extracted, Concentrated, centrifugal ultrafiltration, resin separation, elution, and purification to obtain chlorogenic acid. There are certain problems: without the degreasing step, Product fluidity will be affected; extraction temperature is too high (about 90 °C), which will cause loss of chlorogenic acid.

Although the currently reported techniques also use supercritical technology to treat coffee beans, they are used to remove caffeine from coffee beans. The conditions of supercritical technology affect the content and yield of active ingredients (such as chlorogenic acid); : The United States Gen Foods Corp patent application (EP 19800304045, publication date: June 3, 1981) mentioned that the temperature applied to supercritical technology is above 70 ° C, the main purpose of this technology is to reduce caffeine in green coffee beans The extraction of the main component chlorogenic acid and the content and yield of the extracted product are not considered.

Therefore, if a production method can be developed, the method is simple in operation, and the caffeine is removed while ensuring that the content of the active ingredient (chlorogenic acid) is not lost; the obtained extract product has high chlorogenic acid content and high yield. , no harmful solvent residues, low pesticide residues, good fluidity, and suitable for industrial production, it is bound to have great application prospects and economic value. Summary of the invention

In order to solve the above technical problems, it is an object of the present invention to provide a method for producing a green coffee bean extract.

Another object of the present invention is to provide a green coffee bean extract.

In order to achieve the above object, the method for producing a green coffee bean extract provided by the present invention comprises: subjecting a green coffee bean raw material to supercritical carbon dioxide treatment, and then extracting it with an organic solvent, that is, obtaining.

Wherein the carbon dioxide supercritical treatment comprises a combination of static and dynamic extraction.

Wherein, the carbon dioxide supercritical treatment comprises a two-stage analytical process.

Using the carbon dioxide supercritical technology of the present invention, it is possible to simultaneously remove oil and fat substances

(such as coffee bean oil) and caffeine; and the use of static extraction, which has the advantage of extracting on one hand, and energy consumption on the other hand.

Wherein, in the supercritical treatment of carbon dioxide, extraction by static extraction and dynamic extraction The temperature is 30~60 °C; the extraction temperature of static extraction is preferably 30~50 °C, and the extraction temperature of dynamic extraction is preferably 45~60 °C. The extraction temperature of static and dynamic extraction can be the same or different, and the operation is convenient when the temperature is the same.

Wherein, in the supercritical carbon dioxide treatment, the analytical temperature of the two-stage analysis is 30 to 50 °C.

Further, the temperature of the two-stage analysis may be the same or different. When the temperature of the two-stage analysis is not the same, the first-stage resolution temperature is preferably 40 to 50 ° C, and the second-stage resolution temperature is preferably 30-35 ° C; When the temperature is the same, the resolution temperature is preferably 35 to 45 °C.

Wherein, in the supercritical treatment of carbon dioxide, the conditions of static extraction further include: the extraction pressure is 8~12 MPa, and the extraction time is 20~30 minutes.

Wherein, in the supercritical treatment of carbon dioxide, the conditions of dynamic extraction further include: the extraction pressure is 21~30 MPa, and the extraction time is 3-7 hours.

Wherein, in the supercritical treatment of carbon dioxide, in the dynamic extraction, the mass ratio of the solvent carbon dioxide to the green coffee bean raw material is 10:1~70:1.

Wherein, in the supercritical treatment of carbon dioxide, the two-stage analysis conditions further include: the first-stage analytical pressure is 7.5~10 MPa, and the second-stage analytical pressure is 4~6 MPa.

In the present invention, during the supercritical treatment of carbon dioxide, the carbon dioxide flow rate is 1000-1500 L/h.

Among them, 釆 is extracted with an organic solvent, and the conditions include: setting the ratio of material to liquid (ie, mass to volume ratio of green coffee bean raw material to organic solvent) is 1:3~1:5; extraction temperature is 40~60°C, preferably 45~ 50 ° C; extraction 2 to 5 times, preferably 4 times; each extraction time, the extraction time is 1 to 2 hours, preferably 1.5 hours. The conditions for each extraction can be the same or different, and the operation is convenient when the conditions are the same.

Wherein, the hydrazine is extracted with an organic solvent, and the organic solvent has a water content of 20 to 50%. Wherein, the hydrazine is extracted with an organic solvent which is an alcohol or a ketone solvent. At each extraction, the organic solvents used may be the same or different, and the operation is convenient at the same time.

Further, the alcohol solvent is ethanol or isopropanol. Further, the ketone solvent is acetone.

The method for producing a green coffee bean extract according to the present invention, further comprising: rolling the green coffee bean raw material before the green coffee bean raw material is subjected to carbon dioxide supercritical treatment.

Wherein, the green coffee bean raw material is rolled, including: the green coffee bean raw material is treated with water at 50 to 60 ° C for 10 to 20 minutes, preferably 15 to 20 minutes, and then rolled.

Among them, green coffee beans are rolled into raw materials, and water accounts for 10 to 30% of the quality of green coffee beans. Among them, the green coffee bean raw material is rolled, and the parameters of the rolling equipment used are set to a sheet thickness of 0.1-0.3 mm.

Further, the green coffee bean raw material is rolled, and the water is pure water, and the function is to humidify and soften the green coffee bean raw material.

The method for producing a green coffee bean extract according to the present invention, after extracting with an organic solvent, further comprises: purifying the extract obtained by extracting the hydrazine with an organic solvent with a ceramic membrane.

The extract obtained by extracting with an organic solvent is purified by a ceramic membrane, and comprises: filtering the extract with a ceramic membrane having a filtration precision of 10 to 50 KDa, and the temperature at the filtration is 25 to 35 °C. The purpose of filtration with ceramic membranes is to remove proteins, sugars and microbial impurities.

In the method for producing a green coffee bean extract according to the present invention, the extract obtained by extracting with an organic solvent is purified by a ceramic membrane, and then concentrated under reduced pressure to obtain a paste; the paste is vacuum dried and pulverized. Get a green coffee bean extract product.

Wherein, the mixture is concentrated under reduced pressure to obtain a paste, wherein the conditions for concentration under reduced pressure include: a gas phase temperature of 55 to 65 ° C, preferably 55 ° C; and a degree of vacuum of -0.08 0.1 MPa.

Among them, the temperature of the vacuum drying of the paste is 50-60 ° C, the degree of vacuum is -0.08 ~ -0.1 MPa; the paste is pulverized to 80-100 mesh.

The green coffee bean extract provided by the invention contains the following mass percentage components: 5-CQA (5-caffeoylquinic acid) is 28-37%, 3-CQA (3-caffeyl) Quinine is 2~7%, 4-CQA (4-caffeoylquinic acid) is 2~6%, 3.4- diCQA (3,4-dicaffeoylquinic acid) is 0.2-4%, 3,5-diCQA (3,5-dicaffeoylquinic acid) is 0.2~4%, 4,5-diCQA ( 4,5-dicaffeoylquinic acid) is 0.15 to 2%.

Preferably, the present invention provides a green coffee bean extract having the following mass percentage components: 5-37% for CQA, 2.0-2.7% for 3-CQA, and 3.7 for 4-CQA. ~4.6%, 3,4-diCQA is 1.0~1.3%, 3,5-diCQA is 3.0~4.0%,

4.5- diCQA is from 1·2 to 1.7%.

Among them, 5-CQA is preferably 34 to 37%.

The green coffee bean extract provided by the invention has a total content of chlorogenic acid in the extract product of 45 to 60%; preferably 54 to 60%.

In the present invention, the amount of total chlorogenic acid and the amount of each chlorogenic acid isomer are calculated based on the green coffee bean extract product.

The green coffee bean extract provided by the invention is produced by any of the above methods of the invention, and comprises the following components in mass percentage: 5-CQA (5-caffeoylquinic acid) is 28~37%, 3- CQA (3-caffeoylquinic acid) is 2 to 7%, 4-CQA (4-caffeoylquinic acid) is 2-6%, 3,4-diCQA (3,4-dicaffeoylquinic acid) ) is 0.2-4%, 3,5-diCQA (3,5-dicaffeoylquinic acid) is 0.2-4%, and 4,5-diCQA (4,5-dicaffeoylquinic acid) is 0.15~ 2%.

Preferably, the green coffee bean extract provided by the present invention is produced by any of the above methods of the present invention, and comprises the following components by mass percentage: 5-CQA is 28-37%, 3-CQA is 2.0-2.7% , 4-CQA is 3.7~4.6%, 3,4-diCQA is 1.0-1.3%, 3,5-diCQA is 3·0~4·0%, 4,5-diCQA is 1-2~1·7% .

Among them, 5-CQA is preferably 34 to 37%.

The green coffee bean extract provided by the present invention is produced by any of the above methods of the present invention, wherein the total chlorogenic acid content is 45-60% by mass; preferably 54-60%.

Any of the above-mentioned green coffee bean extracts provided by the present invention mainly contains 28 to 37% of 5-caffeoylquinic acid and 45 to 60% of total chlorogenic acid. In any of the above green coffee bean extracts provided by the present invention, the mass percentage of caffeine is less than 1.5%.

The production method provided by the present invention has the following beneficial effects:

1. Use C0 ₂ supercritical technology instead of hexamethylene and dichloromethane to remove oily substances and caffeine, so that the caffeine content in the extract is less than 1.5%; and the product has no harmful solvent residue, and other solvent residues are also very low ( Less than 50ppm).

2. The supercritical extraction temperature is controlled at 30~60 °C, and the analytical temperature is 30~50 °C, which avoids the influence of high temperature on product content. Because chlorogenic acid is an ester formed by caffeic acid and quinic acid, its molecular structure has three unstable parts: ester bond, unsaturated double bond and polyphenol. If it is in the environment above 70 °C for a long time, it will destroy the molecule. The structure causes a loss of content, which in turn affects the yield of the green coffee bean extract product.

3. The total residue of pesticides such as isoammine, triazophos and dimethoate in the non-supercritical green coffee bean extract product is 3~5 ppm; and the total pesticide of the product treated with the supercritical technology of the invention is Residue below 0.01 ppm, which significantly reduces pesticide residues.

4. Apply specific extraction techniques and conditions to the extraction of specific green coffee beans, and obtain a product with a weight yield of 11% or more. The total chlorogenic acid content of the dried product is 45% or more. 54~60%), the content of single green acid is more than 28% (the effect is 34~37%), and the content of active ingredients is greatly improved.

5. In addition, since the powdery raw material is difficult to be filtered when extracted with an organic solvent, the method of the present invention processes the green coffee bean raw material, and improves the product content and the weight yield relative to the whole bean extract; Powder increases filtration efficiency and reduces production costs.

6. The present invention uses a ceramic membrane to filter and retain a molecular substance having a molecular weight of 50,000 or more to replace the resin to achieve purification of the product; and the solution can be clarified and transparent after the product is dissolved in water.

7. The product obtained by the invention has good fluidity and high quality.

Therefore, the present invention provides a simple and easy method which does not have harmful solvent residues and greatly reduces pesticide residues, and can remove caffeine while ensuring the content of active ingredients. The amount of green coffee bean extract obtained is high, the active ingredient content is greatly improved, the yield is high, the cost is low, which is superior to the prior art, and is suitable for large-scale industrial production, and has great application prospect and economy. value. DRAWINGS

Figure 1 is a flow chart showing the production process of the green coffee bean extract of the present invention. detailed description

The following examples are intended to further illustrate the invention, but are not to be construed as limiting the invention. Modifications or substitutions of the methods, steps or conditions of the invention are intended to be within the scope of the invention.

Unless otherwise specified, the technical means not mentioned in the examples are conventional means well known to those skilled in the art. The first level analysis that occurs is the first level analysis, and the second level analysis is the second level analysis. The detection method of the extract product (liquid phase gradient detection method, which can simultaneously detect the content of each component of chlorogenic acid) and related equipment are also conventional methods and equipment in the art.

The ceramic membrane used in the examples of the present invention is an inorganic filter membrane, which is the product CERMFIL® of Nanjing Jiuwu High-Tech Co., Ltd. The water used is pure water. Other materials used are conventional materials that can be purchased from the market.

In the present invention, the percentage "%" expressed by the content of the active ingredient is a mass percentage. In the present invention, the unit of filtration accuracy KDa is kilodalton. The term "total chlorogenic acid" refers to the general term for all chlorogenic acids or their isomers, and "single chlorogenic acid" refers to 5-CQA. Example 1

Weigh 120 kg of green coffee beans and measure the total acid (ie total chlorogenic acid) content of the raw materials to 7.0%, set the water to 10% of the raw material quality, and soften and soften the water at 60 °C (improve the moisture content of the material). And play the role of entrainer in the subsequent supercritical treatment. After 20min, the sheet is rolled, and the sheet thickness of the rolling mill is 0.1 mm (no loss of raw materials during the rolling process).

The raw material after rolling is supercritically treated by a combination of static and dynamic extraction: static extraction pressure is 8 MPa, extraction time is 20 min; dynamic extraction pressure is 21 MPa, extraction time is 7h; extraction temperature of static extraction is 42 °C, extraction temperature of dynamic extraction is 55 °C; dynamic extraction, the mass ratio of solvent C0 ₂ to green coffee beans after rolling is 70: 1 ; Carbon dioxide supercritical treatment, two-stage analysis: The first-stage analytical pressure is 7.5 MPa, the -stage analytical temperature is 45 °C; the secondary analytical pressure is 4 MPa, and the secondary analytical temperature is 30 °C. The carbon dioxide flow rate is 1000 L/h.

The green coffee bean raw material after supercritical treatment is extracted with 50% (mass fraction) of isopropanol, the mass to volume ratio of the feed liquid is 1:4, the temperature is 45 ° C; the extraction is 4 times, the time of each extraction Both are 1.5h.

The extract obtained by extracting hydrazine with isopropyl alcohol is concentrated under reduced pressure without solvent, and then diluted (conventional conditions), and the diluted solution is filtered with a ceramic membrane having a filtration accuracy of 50 KDa, and the temperature at the time of filtration is 30 ° C; The filtrate was concentrated under reduced pressure at a gas phase temperature of 55 ° C and a vacuum degree of -0.085 MPa to obtain a paste; the paste was vacuum dried at 55 ° C, a vacuum of -0.085 MPa, and pulverized to 90 mesh. After that, the green coffee bean extract product was 13.8 kg; after the product was dissolved in water, the solution was clear and transparent, and the fluidity was good.

The weight yield of the product was 11.50%; the total chlorogenic acid content was 54.7%; the 5-CQA content was 34.2%, the 3-CQA content was 2.46%, the 4-CQA content was 4.21%, and the 3,4-diCQA content was 1.26. %, 3,5-diCQA content is 3.75%, 4,5-diCQA content is 1.53%, other related isomer content is 7.29%; caffeine content is 1.45%; iso-phosphorus, triazophos in product Peptides have a pesticide residue of 0.005 ppm and a solvent residue of 27 ppm. Example 2

Weigh 120 kg of green coffee beans, and test the total acid content of the raw materials to be 6.7%. Set the water to 30% of the raw material quality. After 50 minutes of water softening and softening treatment for 15 minutes, the sheet thickness is set. 0.3 mm.

The raw material after rolling is supercritically treated by a combination of static and dynamic extraction: static extraction pressure is 12 MPa, extraction time is 30 min; dynamic extraction pressure is 30 MPa, extraction time is 3 h; extraction temperature of static extraction At 30 ° C, the extraction temperature of the dynamic extraction is 60 ° C; when the dynamic extraction, the solvent C0 ₂ and the green coffee beans after the rolling The mass ratio is 10:1; carbon dioxide supercritical treatment, two-stage analysis: first-stage analytical pressure is lO MPa, - grade analytical temperature is 40 °C; secondary analytical pressure is 6 MPa, secondary analytical temperature is 30 °C. The carbon dioxide flow rate is 1400 L/h.

The green coffee bean raw material after supercritical treatment is extracted with 70% (mass fraction) ethanol, the mass to volume ratio of the feed liquid is 1:4, the temperature is 50 ° C; the extraction is 4 times, and the extraction time is 1.5. h.

The extract obtained by extraction with ethanol was concentrated under reduced pressure without solvent, and the dilution was filtered through a ceramic membrane having a filtration accuracy of 30 KDa, and the temperature at the filtration was 35 ° C. After filtration and purification, the filtrate was at a gas phase temperature of 55. °C, vacuum degree -0.096 MPa, concentrated under reduced pressure to obtain a paste; the paste was vacuum dried at 50 ° C, vacuum -0.096 MPa and pulverized to 80 mesh, after blending to obtain green coffee bean extract The product is 14.2 kg; the solution is clear and transparent after water-soluble, and the fluidity is good.

The weight yield of the product was 11.83%; the total chlorogenic acid content was 55.6%; the 5-CQA content was 35.03%, the 3-CQA content was 2.5%, the 4-CQA content was 4.28%, and the 3,4-diCQA content was 1.28. %, 3,5-diCQA content is 3.81%, 4,5-diCQA content is 1.56%, other related isomer content is 7.14%; caffeine content is 1.15%; iso-phosphorus, triazophos in product Peptides have a pesticide residue of 0.006 ppm and a solvent residue of 24 ppm. Example 3

Weigh 120 kg of green coffee beans, and test the total acid content of the raw materials to be 6.7%. The set water accounts for 20% of the raw material quality. After 55 minutes of water softening and softening treatment for 15 minutes, the sheet thickness is set. 0.2 mm.

The raw material after rolling is supercritically treated by a combination of static and dynamic extraction: static extraction pressure is 10 MPa, extraction time is 25 min; dynamic extraction pressure is 24 MPa, extraction time is 5 h; extraction temperature of static extraction For 36 ° C, the extraction temperature of dynamic extraction is 54 ° C; when the dynamic extraction, the mass ratio of solvent C0 ₂ to green coffee beans after rolling is 40:1; carbon dioxide supercritical treatment, two-stage analysis: The analytical pressure of the stage is 8 MPa, the analytical temperature of the stage is 50 ° C; the secondary analytical pressure is 5 MPa, the secondary solution The temperature was 35 °C. The carbon dioxide flow rate is 1500 L/h.

The green coffee bean raw material after supercritical treatment is extracted with 80% (mass fraction) acetone, the mass to volume ratio of the feed liquid is 1:4, the temperature is 50 ° C; the extraction is 4 times, and the extraction time is 1.5. h.

The extract obtained by extracting acetone with acetone is concentrated under reduced pressure without solvent, and the diluted solution is filtered with a ceramic membrane having a filtration precision of 10 KDa, and the temperature at the filtration is 25 ° C. After filtration and purification, the filtrate is at a gas phase temperature of 55. °C, vacuum degree -0.09 MPa conditions, concentrated under reduced pressure to obtain a paste; paste is then vacuum dried at 60 ° C, vacuum -0.09 MPa and pulverized to 100 mesh, after blending to obtain green coffee beans extract The product is 13.2 kg; the solution is clear and transparent after water-soluble, and the fluidity is good.

The weight yield of the product was 11.0%; the total chlorogenic acid content was 60.0%; the 5-CQA content was 36.8%, the 3-CQA content was 2.70%, the 4-CQA content was 4.62%, and the 3,4-diCQA content was 1.38. The content of %, 3,5-diCQA is 3.67%, the content of 4,5-diCQA is 1.68%, the content of other related isomers is 9.15%, the content of caffeine is 1.21%, and isoflavin and triazophos in the product. Dimethoate has a pesticide residue of 0.006 ppm and a solvent residue of 18 ppm.

It can be seen from the above examples that the extract products obtained in Examples 1 to 3 have the same effect.

Example 4

120 kg of green coffee beans were weighed and crushed through a 20 mesh sieve to measure the total acid content of the raw materials to be 6.7%.

The pulverized raw material is supercritically treated by a combination of static and dynamic extraction: static extraction pressure is 10 MPa, extraction time is 25 min; dynamic extraction pressure is 24 MPa, extraction time is 5 h; static extraction extraction temperature is At 39 ° C, the extraction temperature of dynamic extraction is 46 ° C. When the dynamic extraction, the mass ratio of solvent C0 ₂ to the green coffee bean raw material after pulverization is 40:1; carbon dioxide supercritical treatment, 两 two-stage analysis: The analytical pressure is 8 MPa, the secondary analytical pressure is 5 MPa, and the two-stage analytical temperature is 40 °C. The carbon dioxide flow rate is 1500 L/h. The green coffee powder powdery material after supercritical treatment is extracted with 80% (mass fraction) acetone, the mass to volume ratio of the feed liquid is 1:3, the temperature is 50 ° C; the extraction is 4 times, and the extraction time is 1.5. h, the extraction of the extract is more difficult.

The extract obtained by extracting acetone with acetone is concentrated under reduced pressure without solvent, and the diluted solution is filtered with a ceramic membrane having a filtration precision of 10 KDa, and the temperature at the filtration is 25 ° C. After filtration and purification, the filtrate is at a gas phase temperature of 55. °C, vacuum degree -0.09 MPa conditions, concentrated under reduced pressure to obtain a paste; paste is then vacuum dried at 60 ° C, vacuum -0.09 MPa and pulverized to 100 mesh, after blending to obtain green coffee beans extract The product is 16.5 kg; the solution is clear and transparent after water-soluble, and the fluidity is good.

The weight yield of the product was 13.75%; the total chlorogenic acid content was 48.7%; the 5-CQA content was 29.8%, the 3-CQA content was 2.19%, the 4-CQA content was 3.75%, and the 3,4-diCQA content was 1.12. %, 3,5-diCQA content is 3.34%, 4,5-diCQA content is 1.36%, other related isomer content is 7.14%; caffeine content is 1.22%; isoflavin, triazophos in product Peptides have a pesticide residue of 0.009 ppm and a solvent residue of 35.8 ppm.

It can be seen from the present embodiment that it is difficult to filter the extract without superfluid treatment after the supercritical treatment; the yield of the product is not affected, but the content of the effective component in the product is lowered.

Example 5

The raw material after rolling is supercritically treated by a combination of static and dynamic extraction: static extraction pressure is 10 MPa, extraction time is 25 min; dynamic extraction pressure is 24 MPa, extraction time is 5 h; static and dynamic extraction extraction The temperature is 45 °C. When the dynamic extraction, the mass ratio of the solvent C0 ₂ to the green coffee bean raw material after rolling is 40:1; the carbon dioxide supercritical treatment, the two-stage analytical analysis: the first-stage analytical pressure is 8 MPa, two The analytical pressure of the stage is 5 MPa, and the analytical temperature of both stages is 38 °C. The carbon dioxide flow rate is 1500 L/h. The green coffee bean raw material after supercritical treatment is extracted with 80% (mass fraction) acetone, the mass to volume ratio of the feed liquid is 1:5, the temperature is 50 ° C; the extraction is 3 times, the first extraction is 2 hours, the first 2. Extract each time for three hours in three times.

The extract obtained by extracting acetone with acetone is concentrated under reduced pressure at a gas phase temperature of 55 ° C and a vacuum degree of -0.09 MPa to obtain a paste; the paste is vacuum dried at 60 ° C under a vacuum of -0.09 MPa. And pulverized to 100 mesh, after the blending, the green coffee bean extract product was obtained 15.1 kg; after the product was dissolved in water, the solution was cloudy and opaque, and the fluidity was not so good.

The product yield was 12.5%; the total chlorogenic acid content was 52.5%; the 5-CQA content was 32.55%, the 3-CQA content was 2.36%, the 4-CQA content was 4.04%, and the 3,4-diCQA content was 1.21. The content of %, 3,5-diCQA is 3.60%, the content of 4,5-diCQA is 1.47%, the content of other related isomers is 7.27%, the content of caffeine is 1.17%, and isoflavin and triazophos in the product. Peptides have a pesticide residue of 0.01 ppm and a solvent residue of 45.7 ppm.

It can be seen from the present example that after the extraction with acetone is carried out, the extraction liquid is not treated by the ceramic membrane, and the solution is turbid and opaque after the water is dissolved; the yield of the product is not affected, but the content of the active ingredient in the product is lowered.

Example 6

The pulverized raw material was supercritically treated by a combination of static and dynamic extraction: static extraction pressure was 10 MPa, extraction time was 25 min; dynamic extraction pressure was 24 MPa, extraction time was 5 h; static and dynamic extraction extraction temperatures were both At 49 ° C; dynamic extraction, the mass ratio of solvent C0 ₂ to pulverized green coffee bean raw material is 40:1; carbon dioxide supercritical treatment, 釆 two-stage analysis: first-stage analytical pressure is 8 MPa, secondary analysis The pressure is 5 MPa and the two-stage resolution temperature is 45 °C. The carbon dioxide flow rate is 1500 L/h.

The green coffee powder powdery material after supercritical treatment is extracted with 80% (mass fraction) of acetone. The mass to volume ratio of the feed liquid is 1:4, the temperature is 50 °C; the extraction is 4 times, and the extraction time is 1.5. h, the extraction of the extract is more difficult. The extract obtained by extracting acetone with acetone was filtered through a 1 μηι bag filter, and the filtrate was concentrated under reduced pressure at a gas phase temperature of 55 ° C and a vacuum of -0.09 MPa to obtain a paste; the paste was further 60 °C, vacuum degree -0.09 MPa vacuum drying and pulverization to 100 mesh, after the preparation of the green coffee bean extract product 17.1kg; after the product water soluble solution turbid opaque, fluidity is not good.

The product yield was 14.25%; the total chlorogenic acid content was 46.2%; the 5-CQA content was 28.6%, the 3-CQA content was 2.08%, the 4-CQA content was 3.56%, and the 3,4-diCQA content was 1.06. %, 3,5-diCQA content is 3.17%, 4,5-diCQA content is 1.29%, other related isomer content is 6.44%; caffeine content is 1.27%; isoflavin, triazophos in product Peptides have a pesticide residue of 0.005 ppm and a solvent residue of 16.8 ppm.

It can be seen from the present embodiment that the raw material is not subjected to the processing of the pulverized sheet, and the extract is filtered by other methods after the extraction with acetone, and the extraction liquid is difficult to be extracted after the supercritical treatment; the yield of the product is not affected, but the product After the water is dissolved, the solution is turbid and opaque; and the content of the active ingredient in the product is lowered. To obtain an extract product having a total chlorogenic acid content of 50%, further purification is required.

Comparative example 1

The raw material after rolling is supercritically treated by a combination of static and dynamic extraction: static extraction pressure is 12 MPa, extraction time is 30 min; dynamic extraction pressure is 30 MPa, extraction time is 3 h; static and dynamic extraction extraction The temperature is 78 °C. When the dynamic extraction, the mass ratio of the solvent C0 ₂ to the green coffee bean raw material after rolling is 10:1; the carbon dioxide supercritical treatment, the two-stage analytical analysis: the first-stage analytical pressure is 10 MPa, two The stage analytical pressure is 6 MPa, and the two-stage analytical temperature is 40 °C. The carbon dioxide flow rate is 1400 L/h.

The green coffee bean raw material after supercritical treatment is extracted with 70% (mass fraction) ethanol, the mass to volume ratio of the feed liquid is 1:4, the temperature is 50 ° C; the extraction is 4 times, each time of extraction The interval is 1.5h.

The extract obtained by extraction with ethanol was concentrated under reduced pressure without solvent, and the dilution was filtered through a ceramic membrane having a filtration accuracy of 30 KDa, and the temperature at the filtration was 35 ° C. After filtration and purification, the filtrate was at a gas phase temperature of 55. °C, vacuum degree -0.096 MPa, concentrated under reduced pressure to obtain a paste; the paste was vacuum dried at 50 ° C, vacuum -0.096 MPa and pulverized to 80 mesh, after blending to obtain green coffee bean extract The product is 11.28 kg; the solution is clear and transparent after water-soluble, and the fluidity is good.

The product yield was 9.41%; the total chlorogenic acid content was 56.7%; the 5-CQA content was 34.8%, the 3-CQA content was 2.55%, the 4-CQA content was 4.37%, and the 3,4-diCQA content was 1.3. %, 3,5-diCQA content is 3.89%, 4,5-diCQA content is 1.59%, other related isomer content is 8.2%; caffeine content is 1.25%; iso-phosphorus, triazophos in product Peptides have a pesticide residue of 0.005 ppm and a solvent residue of 26.8 ppm.

It can be seen from the comparison of the above: In the process of supercritical treatment, if the extraction temperature of static and dynamic extraction is higher, the removal effect of caffeine and pesticide in coffee beans can be achieved, but the weight yield of the product is reduced more. .

Comparative example 2

The raw material after rolling is supercritically treated by a combination of static and dynamic extraction: static extraction pressure is 12 MPa, extraction time is 30 min; dynamic extraction pressure is 30 MPa, extraction time is 3 h; static and dynamic extraction extraction The temperature is 26 °C; when the dynamic extraction, the mass ratio of the solvent C0 ₂ to the green coffee bean raw material after rolling is 10:1; the carbon dioxide supercritical treatment, the two-stage analytical analysis: the first-stage analytical pressure is 10 MPa, two The stage analytical pressure is 6 MPa, and the two-stage analytical temperature is 35 °C. The carbon dioxide flow rate is 1200 L/h.

The extract obtained by extraction with ethanol was concentrated under reduced pressure without solvent, and the dilution was filtered through a ceramic membrane having a filtration accuracy of 30 KDa, and the temperature at the filtration was 35 ° C. After filtration and purification, the filtrate was at a gas phase temperature of 55. °C, vacuum degree -0.096 MPa, concentrated under reduced pressure to obtain a paste; the paste was vacuum dried at 50 ° C, vacuum -0.096 MPa and pulverized to 80 mesh, after blending to obtain green coffee bean extract The product is 16.1 kg; the solution is clear and transparent after water-soluble, and the fluidity is good.

The weight yield of the product was 13.4%; the total chlorogenic acid content was 43.7%; the 5-CQA content was 26.6%, the 3-CQA content was 1.97%, the 4-CQA content was 3.36%, and the 3,4-diCQA content was 1.01. %, 3,5-diCQA content is 3.0%, 4,5-diCQA content is 1.22%, other related isomer content is 6.54%; caffeine content is 8.69%; isoflavin, triazophos in product Peptides have a pesticide residue of 4.2 ppm and a solvent residue of 35.6 ppm.

It can be seen from the comparison of the above: In the process of supercritical treatment, if the extraction temperature of static and dynamic extraction is low, the effect of removing caffeine and pesticide is poor, resulting in high caffeine and pesticide residues in the product; Although the rate does not have much influence, the content of active ingredients in the product is reduced.

Comparative example 3

Weigh 120 kg of green coffee beans and test the total acid content of the raw materials to be 6.7%. The water should be 30% of the quality of the raw materials. After 55 minutes of water softening and softening treatment, the chips are rolled and the thickness of the rolling mill is set. 0.2mm.

The raw material after rolling is supercritically treated by a combination of static and dynamic extraction: static extraction pressure is 12 MPa, extraction time is 30 min; dynamic extraction pressure is 30 MPa, extraction time is 3 h; static and dynamic extraction extraction The temperature is 100 °C; when the dynamic extraction, the mass ratio of the solvent C0 ₂ to the green coffee bean raw material after rolling is 20:1; the carbon dioxide supercritical treatment, the two-stage analytical analysis: the first-stage analytical pressure is 10 MPa, The analytical temperature is 85 °C; the secondary analytical pressure is 6 MPa, and the secondary analytical temperature is 70 °C. The carbon dioxide flow rate is 1300 L/h. The green coffee bean raw material after supercritical treatment is extracted with 70% (mass fraction) ethanol, the mass to volume ratio of the feed liquid is 1:4, the temperature is 50 ° C; the extraction is 4 times, and the extraction time is 1.5. h.

The extract obtained by extraction with ethanol was concentrated under reduced pressure without solvent, and the dilution was filtered through a ceramic membrane having a filtration accuracy of 30 KDa, and the temperature at the filtration was 35 ° C. After filtration and purification, the filtrate was at a gas phase temperature of 55. °C, vacuum degree -0.096 MPa, concentrated under reduced pressure to obtain a paste; the paste was vacuum dried at 50 ° C, vacuum -0.096 MPa and pulverized to 80 mesh, after blending to obtain green coffee bean extract The product is 15.9 kg; the solution is clear and transparent after water-soluble, and the fluidity is good.

The product yield was 13.25%; the total chlorogenic acid content was 40.8%; the 5-CQA content was 25.3%, the 3-CQA content was 1.84%, the 4-CQA content was 3.14%, and the 3,4-diCQA content was 0.94. %, 3,5-diCQA content is 2.8%, 4,5-diCQA content is 1.14%, other related isomer content is 5.64%; caffeine content is 1.32%; isoflavin, triazophos in product Peptides have a pesticide residue of 0.008 ppm and a solvent residue of 45.8 ppm.

It can be seen from the present comparison that in the process of supercritical treatment, if the extraction temperature of the static and dynamic extraction is high, and the analytical temperature is also high, the content of the active ingredient is largely lost, that is, the content of the active ingredient is low.

Although the present invention has been described in detail with reference to the preferred embodiments of the present invention, it will be apparent to those skilled in the art. Therefore, such modifications or improvements made without departing from the spirit of the invention are intended to be within the scope of the invention. Industrial applicability

The invention provides a method for producing a green coffee bean extract, which comprises: subjecting a green coffee bean raw material to supercritical treatment of carbon dioxide, and then extracting with an organic solvent, that is, obtaining. The obtained green coffee bean extract product mainly contains 28-37% of 5-caffeoylquinic acid and 45~60% of total chlorogenic acid, and has pharmacological effects such as anti-oxidation, anti-virus, anti-cancer, antibacterial or cellulite. active.

Claims

claims

1. A method for producing green coffee bean extract, including: subjecting green coffee bean raw materials to carbon dioxide supercritical treatment, and then extracting them with organic solvents to obtain the green coffee bean extract.

2. The production method of green coffee bean extract according to claim 1, characterized in that the carbon dioxide supercritical treatment includes static extraction, dynamic extraction and two-stage analysis; the extraction temperatures of both static extraction and dynamic extraction are 30~60°C; the extraction temperature for static extraction is preferably 30~50°C, and the extraction temperature for dynamic extraction is preferably 45~60°C;

The desorption temperatures of the two-stage analysis are both 30~50°C; when the temperatures of the two-stage analysis are different, the first-stage analysis temperature is preferably 40~50°C, and the second-stage analysis temperature is preferably 30~35°C; when the two-stage analysis When the temperatures are the same, the desorption temperature is preferably 35~45°C.

3. The production method of green coffee bean extract according to claim 2, characterized in that, in the static extraction, the extraction pressure is 8~12 MPa, and the extraction time is 20~30 minutes;

In the dynamic extraction, the extraction pressure is 21~30 MPa, the extraction time is 3~7 hours, and the mass ratio of carbon dioxide to green coffee bean raw materials is 10: 1~70: 1;

In the two-stage analysis, the first-level analysis pressure is 7.5~10 MPa, and the second-level analysis pressure is 4-6 MPa.

4. The production method of green coffee bean extract according to any one of claims 1 to 3, characterized in that, in the carbon dioxide supercritical treatment, the carbon dioxide flow rate is 1000-1500 L/h.

5. The production method of green coffee bean extract according to any one of claims 1 to 4, characterized in that, an organic solvent is used for extraction, and the conditions include: The mass and volume ratio of the green coffee bean raw material and the organic solvent is 1: 3~1:5, the extraction temperature is 40~60°C, preferably 45~50°C; 2 to 5 times of extraction, 1 to 2 hours each time; preferably 4 times of extraction, 1.5 hours each time.

6. The method for producing green coffee bean extract according to claim 1 or 5, characterized in that the organic solvent is an alcohol or ketone solvent; the water content of the organic solvent is 20 to 50%.

7. The method for producing green coffee bean extract according to claim 6, wherein the alcohol solvent is ethanol or isopropyl alcohol, and the ketone solvent is acetone.

8. The production method of green coffee bean extract according to any one of claims 1 to 7, characterized in that, before subjecting the green coffee bean raw material to carbon dioxide supercritical treatment, it further includes: rolling the green coffee bean raw material into flakes .

9. The production method of green coffee bean extract according to claim 8, characterized in that: the green coffee bean raw material is rolled into flakes, including: the green coffee bean raw material is treated with water at 50~60°C for 10 Roll into flakes after ~20 minutes; water accounts for 10~30% of the mass of green coffee beans, and the thickness of the rolled flakes is 0.1~0.3 mm.

10. The method for producing green coffee bean extract according to any one of claims 1 to 9, characterized in that, after extraction with an organic solvent, it further includes: refining the extraction liquid with a ceramic membrane.

11. The production method of green coffee bean extract according to claim 10, characterized in that, refining the extraction liquid with a ceramic membrane, including: filtering the extraction liquid with a ceramic membrane with a filtration accuracy of 10 to 50 KDa, The temperature during filtration is 25~35°C.

12. The production method of green coffee bean extract according to claim 10 or 11, characterized in that, after the extraction liquid is refined with a ceramic membrane, it is concentrated under reduced pressure to obtain a paste; and the paste is then vacuum-processed Dry and crush to obtain a green coffee bean extract product; the conditions for the reduced pressure concentration include: gas phase temperature is 55~65 °C, vacuum degree is -0.08-0.1 MPa; the temperature for vacuum drying of the paste is 50~60 °C, the vacuum degree is -0.08-0.1 MPa; crush the paste to 80-100 mesh.

13. A green coffee bean extract produced by the production method of the green coffee bean extract described in any one of claims 1 to 12, which contains the following ingredients in mass percentage: 5-caffeoylquinic acid is 28~37%, 3-caffeoylquinic acid is 2~7%, 4-caffeoylquinic acid is 2~6%, 3,4-dicaffeoylquinic acid is 0.2~4%, 3,5 -Dicaffeoylquinic acid is 0.2~4%, 4,5-dicaffeoylquinic acid is 0.15~2%; the 5-caffeoylquinic acid is preferably 34~37%.

14. A green coffee bean extract containing the following ingredients in mass percentage: 5-caffeoylquinic acid is 28~37%, 3-caffeoylquinic acid is 2~7%, 4-caffeoylquinic acid is Nic acid is 2~6%, 3,4-dicaffeoylquinic acid is 0.2~4%, 3,5-dicaffeoylquinic acid is 0.2-4%, 4,5-dicaffeoylquinic acid is It is 0.15~2%; the 5-caffeoylquinic acid is preferably 34~37%.

15. The green coffee bean extract according to claim 13 or 14, characterized in that the mass percentage of total chlorogenic acid is 45~60%, preferably 54~60%.

16. The green coffee bean extract according to any one of claims 13 to 15, characterized in that the mass percentage of caffeine is less than 1.5%.