WO2003028481A1

WO2003028481A1 - Method of preparing lycopene

Info

Publication number: WO2003028481A1
Application number: PCT/CN2002/000080
Authority: WO
Inventors: Huanzhong Chen
Original assignee: Xinjiang Jinqi Industry Limited
Priority date: 2001-09-28
Filing date: 2002-02-09
Publication date: 2003-04-10
Also published as: CN1118521C; CN1341686A

Abstract

The invention relates to a method of preparing natural lycopene having a degree of crystallinity of more than 80% from tomato puree as raw material, said method comprises : first, extracting the material with low-molecular weight alcohol solvents ; separating to remove water, resins, volatile oils, saccharides, baregins, and the like ; then extracting lycopene with organic solvents ; allowing crystalline lycopene separate out during recovering the solvents. Advantages of the present method is simple and convenient, high efficient, and energy saving.

Description

Preparation method of lycopene

Technical field

The invention relates to a method for preparing lycopene, and in particular to a method for preparing a high-purity natural lycopene with lycopene crystals of 80-90% by using a ketchup product as a raw material, a simple method, and a high yield. method. Background technique

Lycopene belongs to the class of carotenoids and is widely found in nature. Its most important natural source is tomato. It has been used as a food, feed, cosmetic and pharmaceutical additive a lot. For example, lycopene crystals can be used as an important raw material for the production of natural anti-cancer drug preparations such as prostate cancer and breast cancer; they can be used as natural health foods (such as soft gelatin, water-soluble microcystin, Oral liquids, lozenges, etc.) additives; can also be used as food, color cosmetics for advanced cosmetics (such as lipstick, rouge, etc.).

Because of the wide use of lycopene, there have been many research reports on the preparation of natural lycopene. The raw materials for its production are mainly fresh tomatoes (lycopene content greater than 1QGppm) or tomato products (such as tomato sauce, tomato powder, etc.) and Scraps from tomato products (tomato peel, dregs). Compared with other carotenoids, lycopene has the antioxidant properties and color stability of its coarse-crystalline products. Therefore, the production of lycopene requires a purification process to achieve high stability with high purity. Nature. At present, there are publicly disclosed methods for producing natural lycopene. Generally, at least twice the organic solvent is used to heat the tomato or ketchup raw material (50-6 (TC)) extraction. First, the lycopene containing 2-5% Oleoresin, and then select an appropriate solvent to extract the oleoresin, the crude lycopene crystals obtained are then washed with the solvent multiple times, the whole process is long, and the number of operation steps is not only high energy consumption, but also leads to The rate is low, for example, the method described in PCT application PCT / US95 / 14475, it takes 4-6 hours from feeding to crystallization, and the yield is only 64.72% (Example 1), that is, the tomato in the raw material after the process The total loss of lycopene is as high as 35. 28%. Another example is that CN1298904A can only obtain 24% lycopene-containing crystals from 6-10 hours from feeding to crystallization, and the total yield is only 19.5%. 80. 5% or more (Example 1). Similar conclusions can be obtained by studying the technical descriptions and examples in other public documents, such as Gu 44831, EP-A-382067, EP-000140, PCT / W097 / 48287, etc. Summary of invention

The purpose of the present invention is to provide an innovative process for the disadvantages of long production processes and low product yields in the prior art. The tomato or tomato product is used as a raw material to prepare crystallinity of more than 80%, especially 90%. In the above lycopene, the whole process is simple and easy to operate, and the energy consumption is low, but the yield is significantly higher than that of the prior art method, thereby achieving the purpose of high efficiency and energy saving.

According to the method of the present invention, lycopene is used to dissolve a variety of fat-soluble solvents and oils, but is only slightly soluble in low-carbon alcohols such as ethanol (heated) and hardly soluble in cold ethanol. First, low-molecular alcohol solvents are used. Remove the moisture in tomatoes or tomato products, and some resins, volatile oils, sugars, viscose and certain alkaloids, pigments (yellow pigments) and glycosides, increase the lycopene content in the raw materials, and then use Organic solvents extract it from the raw materials, and the lycopene crystals can be directly precipitated during the solvent recovery process. Compared with the prior art method, the process of the present invention is obviously tubular, and can be directly precipitated in the process of recovering the extraction solution without undergoing the oleoresin preparation process, and has a high crystallinity of lycopene, and the yield is greatly improved.

The preparation method of the lycopene proposed by the present invention uses tomato ketchup with a water-soluble solid content of 28-38% as a raw material. The preparation method includes the following steps:

1) The tomato sauce raw material is extracted at room temperature with an alcohol solvent having less than 4 carbons and a concentration of more than 70%. The amount of the alcohol solvent is 5 to 10 times the weight of the tomato sauce raw material. The insoluble matter separated is at 30-36 ° C. Dry under vacuum to make fibrous 4-fragment material with water content of 1-5%;

2) Extract the powdery material in step 1) at room temperature with an organic solvent that can dissolve lycopene and has a boiling point below 80 ° C, and recover the solvent in the extract at 26-52 ° C to precipitate crystals.

Practice has proven that using tomato sauce to produce natural lycopene is the most economical and reasonable option. Compared with fresh tomatoes, it has a high lycopene content (about 400-600 ppm), cheap raw materials, convenient storage, and is suitable for industrial mass production. Therefore, the present invention selects tomato sauce as a raw material, wherein the content of water-soluble solids is 28-38%, including various specifications of tomato sauce prepared from different tomato varieties, such as lycopene Content of the feedstock in the tomato sauce 45- 70mg / 100g or more, orange-red tomato powder or lycopene in the lycopene content of the red pigment Ru ^{2 00mg} / 100g of tomato pomace powder 30- 40mg / 100g of fresh tomatoes may be used However, it should first be thermally broken to separate the skin and seeds, and centrifuged to dehydrate to a wet slag containing less than 70% water.

In the present invention, a low-carbon alcohol solvent, preferably ethanol, is used to remove moisture and impurities from tomato sauce under normal conditions (without heating), and the lycopene-containing fibrous fine powder containing lycopene is obtained by drying at low temperature. raw material. Due to the different solubility of many impurity components in the raw materials of ketchup in different concentrations of alcohol, the extraction process preferably uses different concentrations of alcohol solvents to sequentially extract and separate various types of miscellaneous shields, for example, first use 70-95% ethanol , Generally, it is extracted by stirring for 5-15 minutes, and the insoluble matter is separated. Use an ethanol solvent with a concentration of more than 95% (especially 99.7% anhydrous ethanol) and extract again for 3-10 minutes.

According to the preparation method provided by the present invention, since components that affect the lycopene extraction rate are removed in advance, the lycopene content in the raw material is significantly increased, and resins, pigments and viscous components no longer exist, as long as organic solvents are used under normal conditions The extraction of lycopene can be realized, and the extraction process can be completed quickly as long as it is fully stirred. From the perspective of extracting lycopene, all organic solvents that can dissolve lycopene and have a boiling point lower than 8 ° C can be used, but from the perspective of the application of the product, the present invention preferably uses a food-grade non-toxic product that can be used for food production. Solvents such as carbon disulfide, toluene, benzene, chloroform, dichloromethane, etc., although lycopene can also be dissolved, in order to avoid toxic solvent residues in crystalline products, it is generally not selected. The present invention preferably uses methyl acetate ( Boiling point 55-58 ° C), ethyl acetate (boiling point 77.ire) or a mixture thereof.

According to the method of the present invention, it is preferred to use a low-boiling point organic solvent with a weight of 3 to 8 times the weight of the powdery material for two or three extractions. The filter residue after the first extraction is added to the solvent extraction again, and the extraction solution is extracted. merge. The solvent recovery temperature is preferably controlled at 26-38 ° C. When the solvent evaporates 60-70%, it can be seen that a large number of fine flake lycopene begins to crystallize out. Until 90-95% of the solvent is recovered, lycopene Also about 90-95% has crystallized out. The equipment for solvent recovery and precipitation crystallization process can be selected from centrifugal falling film vacuum evaporator, direct heat pump evaporator, falling film vacuum evaporator, rising film vacuum evaporator, DTB high-efficiency vacuum crystallizer, rotary thin film evaporator, etc. For conventional chemical equipment, a centrifugal falling film vacuum evaporator and a DTB high-efficiency vacuum crystallizer are preferably used. The precipitated crystals are added to, for example, washed with absolute ethanol (usually in an enamel or stainless steel reaction tank with a stirrer) to remove residual yellow pigment or other impurities, and the crystals are filtered and dried again. That is, the preparation method of the present invention further includes The purification process of the crystals precipitated in step 2) and the dried crystals is washed with absolute ethanol or anhydrous methanol. When the crystals are washed until light yellow to colorless, the solvent is filtered off with a 500-mesh filter cloth, and dried to form a dark copper fine powder (particle size 10-180 μm) lycopene crystals, wherein the lycopene content is between Above 80%, it can be as high as 90%. According to a preferred embodiment of the present invention, the method for drying and washing the crystals includes: blast drying at room temperature for 20-40 minutes, for example, placing in a blast drying box for 20-40 minutes at room temperature at 20-36 ° C; controlling 30-36 Ό Dry under vacuum (-0. 08-0. 098MPa) for 15-30 minutes, or dry naturally at room temperature for 4-6 hours.

The lycopene crystal of the present invention can be packed in a pressure-resistant glass bottle or an aluminum-plastic composite bag under vacuum (-0. 09Mpa) or filled with nitrogen (purity 99.9%). Stable for a long time without deterioration (the discoloration process is the deterioration process, the crystal changes from dark copper with metallic luster to red, orange, dark yellow, yellow, and finally milky white, indicating that the lycopene content has gradually degraded to zero).

As mentioned above, the present invention provides a method for preparing lycopene that is different from the prior art. Before extraction, the unnecessary components in the tomato raw material are first separated and removed, and the oleoresin is not first extracted, and then the oleoresin is removed. In the process of extracting and concentrating lycopene crystals, the low-temperature concentration of the normal temperature leaching solution of the organic solvent is used to precipitate the target product lycopene crystals during the solvent recovery process. It is no longer necessary to cool to -15 ° C for crystallization, which facilitates purification. . The method of the present invention removes other components of the tomato sauce raw material to the greatest extent (effectively retains lycopene in the raw material), greatly improves the lycopene content in the raw material, and improves the extraction of lycopene while simplifying the process. The measurement shows that the lycopene extraction rate of the present invention can reach more than 85%. In the method of the present invention, the temperatures of raw material treatment, solvent recovery and crystal dissolution are not more than 50 ° C, preferably not more than 36 ° C. Compared with the prior art method, the energy consumption can be significantly reduced.

The method of the present invention can prepare lycopene crystals with a crystallinity higher than 80%, especially higher than 90%. Its high purity provides relatively high stability, and can be stable for a long time without degradation under appropriate conditions. With its application in antitumor drug preparations and health foods, biological and enzyme pollution can be effectively prevented without the use of antioxidants, preservatives, and the like. detailed description

The following further describes the implementation of the technical solution of the present invention with specific examples, but does not limit the scope of implementation of the present invention. Example 1

Method for preparing lycopene containing 80-90% crystals by using tomato sauce

Put 100kg of 28-30 size tomato sauce containing lycopene 50mg / l G0 into a 500L paddle-type stainless steel stirring pot, add 300kg of 95% ethanol, stir for 10min, and centrifuge for 5min with a centrifuge to solidify the tomato paste residue after centrifugation 8kg light purple red with tomato red, add 100kg 99% absolute ethanol, stir for 5min, centrifuge with a speed of 1600-3000r / min in a centrifuge, heat at 36 ° C with a conical rotary vacuum dryer, and dry for 20min. 382mg / 100g (method for measuring lycopene is known, the present invention will not be described in detail) a fibrous fine particle powdery raw material.

Put 12.8 kg of the above-mentioned lycopene-containing 382 mg and 800 g of raw materials into a 100 L stainless steel stirring pot and add 95 ° /. Methyl acetate was extracted by stirring at 38.2 kg for 15 min and centrifuged at 1600-3000 r / min to obtain a primary extraction solution and filter residue. The filter residue was placed in the above stirring pot and added with 95% methyl acetate at 20 kg. 6mg 八 00g。 Liquid, combined two extractions for a total of 54kg, fine filtration with filter paper, the fine filtration to obtain a deep red clear extract, containing lycopene is 86.6mg 八 00g.

The above 53.8 kg of extraction liquid was continuously fed into a centrifugal falling film vacuum (-0.09Mpa) evaporator heated at a rate of about 1 kg per minute to recover methyl acetate solvent in about 50 minutes to collect lycopene. Crystal 48.2g, lycopene content was 89.2%.

Lycopene yield lycopene crystal weight (g) x lycopene content (¾) x 100%

Ingredient weight X Lycopene content 00

48.2g X 89.2% X 100% = 43g X 100%

l OOOOOg X 50mg / 100g 50g Example 2

Method for preparing lycopene containing 80-90% crystals by using tomato sauce

Put 100kg of 36/38 tomato sauce containing 56mg / 100g of lycopene into a 500L paddle-type stainless steel stirring pot, add 400kg of 95% ethanol, stir for 20min, and release it with a 1600-3000r / min centrifuge for 5min. The slag solid was added to the above pot and 100 kg of 99% absolute ethanol was added and stirred for l Omin: Centrifuge with a 1600-3000r / min centrifuge, and mix and dry with a conical rotary vacuum dryer 30-36 ° C for 20min to obtain 14.6kg light purple red Contains lycopene 357.5g / 100g fiber shield fine particles powdery raw material.

Put 14.6 kg of lycopene-containing 357.5 mg / 100 g of raw materials into a 100L stainless steel mixing pot and add

98% ethyl acetate 35. 4kg with stirring and extraction for 15min and release, centrifugation with a 1600-3000r / min centrifuge to obtain an extraction solution and filter residue, put this filter residue into the above stirring pot and add 98% ethyl acetate 20kg with stirring for 5min and release A second extraction liquid was obtained, and the two extraction liquids were combined for a total of 52.8 kg, and then the extraction liquid was finely filtered with filter paper to obtain 52.6 kg of a deep red ethyl acetate clear extraction liquid, containing 94.2 mgA 00g of lycopene.

The above 52.6 kg of the extract was placed in a 100L stirred stainless steel tank with a vacuum degree (-0.098mpa) and heated at 48 ° C for 1.2 hours to recover the ethyl acetate solvent to obtain 60.2 g of lycopene crystals and a lycopene content of 83. 3%. The yield of lycopene is'. Lycopene crystal weight (g) X lycopene content (%) X 100%

Ingredient weight X Lycopene content (%)

= 60. 2g X 83.3 ° /. X 100% = 50. 14g X 100% = 89. 5% l OOOOOg X 56mg / 100g 56g Example 3

Method for preparing lycopene containing more than 96% crystals by using tomato sauce

Put 100kg of 28/30 tomato sauce containing 52mg / 100g of lycopene into a 500L paddle-type stainless steel stirrer, stir in 300kg 90% ethanol, stir for 10 minutes, and centrifuge in a 3000r / min centrifuge for 5min. Put the sauce solid into the above pot, add 100kg of 99% absolute ethanol, stir for 10min, release, centrifuge with 3000r / min centrifuge, mix and dry with conical rotary vacuum dryer for 20min at 30 ° C to get 12kg light purple red containing lycopene 423mg 80Q _g fibrous fine particles powdery raw material. Put 12kg of lycopene containing 423mg / 100g of raw materials into a 100L stainless steel stirrer, add 95% ethyl acetate and 99% ethyl acetate, 30kg each, heat at 30 ° C, stir and extract for 20min, and release 51kg of extract once. Heat in the above stirring pot at 30 ° C, add 99% ethyl acetate, 20kg, stir and extract, and centrifuge to obtain 20kg of secondary extract by centrifugation at 3000r / min. Combine the two extracts for a total of 77kg, and finely filter to obtain clear dark red methyl acetate. 0mg / 100g。 Ester and ethyl acetate mixed extract 76.8kg, lycopene content of 63.0mg / 100g.

4g The above 76.8kg extract was continuously fed into a centrifugal falling film vacuum (-0.09mpa) evaporator heated at a speed of about 1kg per minute to recover the solvent for about lh to obtain crystalline lycopene 48.4g 2%。, Washed once with absolute ethanol, vacuum -0.098Mpa for 30min and crystallized into a fine powder with a lycopene content of 96.2%. Lycopene yield lycopene crystal weight (g) X lycopene content ()

Ingredient weight X Lycopene content (%)

= 48.4 g X 96. 2¾ X 100% = 46.5 g χ 100% = 89.4%

lOOOOg x 52mg / 100g 52g

Claims

Rights request

1. A method for preparing lycopene, characterized in that tomato sauce with a water-soluble solid content of 28-38% is used as a raw material, and the method includes the following steps:

1) Remove the water and non-lycopene impurities in the tomato sauce raw materials with an alcohol solvent with a concentration of less than 4 carbons and a concentration higher than 70% at room temperature. The amount of the alcohol solvent is 5-10 times the weight of the tomato sauce. The insolubles are dried under vacuum at 30-36 ° C to make a fibrous powder with a moisture content of 1-5%;

2) Use lycopene which is soluble and has a boiling point lower than 8 (TC organic solvent normal temperature extraction step 1), and recover the solvent in the extract at 26-52 ° C to make it crystallize .

2. The method for preparing lycopene according to claim 1, wherein the alcohol solvent for extracting the raw material of the ketchup is ethanol.

3. The preparation method according to claim 1 or 2, wherein the ketchup raw material is extracted twice with an alcohol solvent: 70-95% concentration of alcohol is used first, and insolubles are separated, and then treated with an alcohol solvent with a concentration of 95% or more. .

4. The method according to claim 1, wherein the organic solvent capable of dissolving lycopene and having a boiling point lower than 80 ° C is a food-grade organic solvent.

The method according to claim 4, wherein the organic solvent is selected from the group consisting of ethyl acetate, ethyl acetate, or a mixed solvent thereof.

6. The preparation method according to claim 1, wherein the organic solvent is leached with the organic solvent in an amount of 3-8 times the weight of the powdery material, and the solvent residue is added to the filter residue after the first leaching to obtain The extracts were combined.

7. The production method according to claim 1 or 6, wherein the organic solvent in the extract is recovered by controlling the temperature at 26-38 ° C.

8. The preparation method according to claim 1, further comprising washing the crystals precipitated in step 2) and drying the crystals with anhydrous ethanol.

9. The preparation method according to claim 8, wherein the method for drying and washing the crystals comprises: blasting at room temperature for 20-40 minutes, controlling 30-36, vacuum drying for 15-30 minutes, or natural drying at room temperature for 4 to 6 hours .

10. A lycopene product with a lycopene crystal content of 80-90%, which is prepared by the method of any one of the preceding claims.