Compound solubilizer and liquid non-crystalline oil-soluble oleoresin of capsicum and its preparation method

Abstract

The present invention relates to the technical field of food processing, and in particular, to a composite solubilizer and a liquid non-crystalline oil-soluble oleoresin of pepper and a preparation method thereof. The composite solubilizer is used for preparing the liquid non-crystalline oil-soluble oleoresin of pepper. In terms of mass percentage, it includes 10-20% span, 30-40% glycerol monooleate, and 40-60% isopropyl myristate. The composite solubilizer can effectively remove the components insoluble in oil in the crude oleoresin of pepper, and fully retain the main flavor components of pepper, so that the obtained oleoresin of pepper remains in a stable liquid state, the piperine in the oleoresin of pepper is not easily precipitated, and it has good oil solubility.

Description

Technical Field

[0001] The present invention relates to the technical field of food processing, and more particularly to a composite solubilizer and a liquid non-crystalline oil-soluble oleoresin of pepper and a preparation method thereof. Background Art

[0002] As a spice, pepper has a long history of use in China. In modern food processing, pepper is also an important spice for removing fishy smell and enhancing flavor, and is almost used in the processing of various meats. The existing ways of using pepper include using pepper directly after grinding, or extracting pepper by solvent method or supercritical technology to obtain oleoresin of pepper and then using the oleoresin of pepper. There are certain defects in using pepper by the above methods. For example, the way of using pepper powder needs to consider the influence caused by factors such as microorganisms and impurities, and the large purchase volume and high storage cost limit the use of pepper. The oleoresin of pepper extracted by the solvent method cannot be completely dissolved in oil or water, contains a large amount of substances insoluble in oil, has a viscous state, a large amount of solids precipitate, and is in a solid-like state, which is inconvenient to use. Although the oleoresin of pepper extracted by supercritical extraction can be completely dissolved in oil, due to the high concentration of piperine in it, piperine often crystallizes out, and the melting point of piperine is as high as 130°C, so it needs to be heated first when used, and heating and dissolving will cause the loss of flavor substances and is also inconvenient to use.

[0003] In view of this, the present invention is specifically proposed. Summary of the Invention

[0004] The purpose of the present invention is to provide a composite solubilizer and a liquid non-crystalline oil-soluble oleoresin of pepper and a preparation method thereof. The composite solubilizer provided by the embodiment of the present invention can effectively remove the components insoluble in oil in the crude oleoresin of pepper, and fully retain the main flavor components of pepper, so that the obtained oleoresin of pepper remains in a stable liquid state, the piperine in the oleoresin of pepper is not easy to precipitate, and it has good oil solubility.

[0005] The present invention is implemented as follows:

[0006] In a first aspect, the present invention provides a composite solubilizer, which is used for preparing a liquid non-crystalline oil-soluble oleoresin of pepper. In terms of mass percentage, it includes 10-20% span, 30-40% glycerol monooleate, and 40-60% isopropyl myristate.

[0007] In an optional embodiment, the span is selected from span 80;

[0008] Preferably, in terms of mass percentage, it includes 15% span, 35% glycerol monooleate, and 50% isopropyl myristate.

[0009] Second aspect, the present invention provides a liquid, non-crystalline, oil-soluble piperine oleoresin, the raw materials of which include a crude piperine oleoresin and the composite solubilizer described in the foregoing embodiments.

[0010] In an alternative embodiment, the dosage of the composite solubilizer is 1.5 - 3 times the mass of the crude piperine oleoresin, preferably 2 times.

[0011] In an alternative embodiment, the crude piperine oleoresin is an ethanol-extracted piperine oleoresin;

[0012] Preferably, the liquid, non-crystalline, oil-soluble piperine oleoresin is a liquid piperine oleoresin without solid precipitation after being placed at room temperature for 360 days.

[0013] Third aspect, an embodiment of the present invention provides a method for preparing a liquid, non-crystalline, oil-soluble piperine oleoresin, including: treating a crude piperine oleoresin with the above-mentioned composite solubilizer.

[0014] In an alternative embodiment, it includes: mixing the crude piperine oleoresin and the composite solubilizer, heating, then cooling to precipitate oil-insoluble substances, and then performing solid-liquid separation.

[0015] In an alternative embodiment, the heating temperature is 131 - 140 °C and the time is 5 - 10 minutes;

[0016] Preferably, natural cooling is used for cooling;

[0017] Preferably, the natural cooling time is 24 - 36 hours.

[0018] In an alternative embodiment, the precipitate obtained by solid-liquid separation is pressure-filtered to form a pressure filtrate, and the pressure filtrate is mixed with the supernatant obtained by solid-liquid separation;

[0019] Preferably, the pressure filtration is performed in a sealed environment using food-grade silica as the pressure filtration layer.

[0020] The present invention has the following beneficial effects: In the embodiments of the present invention, the composite solubilizer formed by specific components and ratios can specifically act on the piperine oleoresin, remove the components insoluble in oil in the piperine oleoresin, and at the same time can fully retain the flavor substances of pepper, so that the formed piperine oleoresin remains in a stable liquid state. Even if the piperine oleoresin is placed for a long time, no solids, such as piperine, will precipitate, and it can be directly used, and the piperine oleoresin has good oil solubility. Detailed Embodiments

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. Those not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. Reagents or instruments not indicated with the manufacturer are all conventional products that can be obtained through commercial purchase.

[0022] An embodiment of the present invention provides a composite solubilizer. In terms of mass percentage, it includes 10-20% of Span, 30-40% of glyceryl monooleate, and 40-60% of isopropyl myristate.

[0023] For example, 15% of Span, 35% of glyceryl monooleate, and 50% of isopropyl myristate; 20% of Span, 32% of glyceryl monooleate, and 48% of isopropyl myristate; 10% of Span, 40% of glyceryl monooleate, and 50% of isopropyl myristate; 10% of Span, 30% of glyceryl monooleate, and 60% of isopropyl myristate; 13% of Span, 37% of glyceryl monooleate, and 50% of isopropyl myristate; 17% of Span, 38% of glyceryl monooleate, and 45% of isopropyl myristate; 13% of Span, 32% of glyceryl monooleate, and 55% of isopropyl myristate, etc.

[0024] Specifically, Span can be selected from any value between 10% and 20% such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, and 20%, or a range value formed by any two values.

[0025] Glyceryl monooleate can be selected from any value between 30% and 40% such as 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, and 40%, or a range value formed by any two values.

[0026] Isopropyl myristate can be selected from any value between 40% and 60% such as 40%, 43%, 45%, 47%, 48%, 49%, 50%, 52%, 55%, 57%, 59%, and 60%, or a range value formed by any two values.

[0027] Among them, Span is selected from Span 80. In the embodiments of the present invention, only Span 80 is used as an example, and other Spans can be selected. The selected glyceryl monooleate and isopropyl myristate are all existing purchasable raw materials.

[0028] In the prior art, solubilizers are also used to treat oleoresin piperis, but even after treating oleoresin piperis with solubilizers, solid substances are still likely to precipitate after long-term storage, and it is easy to cause loss of flavor substances of pepper. However, the composite solubilizer provided by the embodiments of the present invention can specifically treat oleoresin piperis, not only can effectively remove the oil-insoluble substances in oleoresin piperis, but also can fully retain the flavor substances of pepper. Moreover, the oleoresin piperis treated with the composite solubilizer has good stability and no solid will precipitate after long-term storage. At the same time, the oleoresin piperis has good oil solubility.

[0029] Second, the present invention provides a liquid and non-crystalline oil-soluble oleoresin piperis, the raw materials of which include a crude oleoresin piperis and the composite solubilizer described in the foregoing embodiment.

[0030] Among them, the dosage of the composite solubilizer is 1.5-3 times the mass of the crude oleoresin piperis, preferably 2 times. Using the above ratio can not only ensure the effect of the composite solubilizer in dissolving the crude oleoresin piperis, but also ensure the content of flavor substances. If the ratio is lower than this, the crude oleoresin piperis may not be dissolved sufficiently, and the formed oleoresin piperis may still contain a large amount of oil-insoluble substances, affecting the stability of the oleoresin piperis. If the ratio is higher than this, the content of flavor substances will be affected.

[0031] Furthermore, the crude oleoresin piperis is an alcohol-extracted oleoresin piperis. The alcohol-extracted oleoresin piperis used in the present invention is only an example of the embodiments of the present invention, and the crude oleoresin piperis obtained by supercritical extraction can also be selected. At the same time, the crude oleoresin piperis can be self-made or purchased.

[0032] For example, in the embodiments of the present invention, the pepper raw materials are subjected to low-temperature percolation extraction with alcohol (such as 90% ethanol), and then the extract is collected, concentrated until there is no alcohol smell, and then naturally cooled to remove clear water to obtain the crude oleoresin piperis.

[0033] The liquid and non-crystalline oil-soluble oleoresin piperis is a liquid oleoresin piperis without solid precipitation after standing at room temperature for 360 days.

[0034] Third, the embodiments of the present invention provide a preparation method for a liquid and non-crystalline oil-soluble oleoresin piperis, including:

[0035] S1. Form a crude oleoresin piperis;

[0036] Take an alcohol solvent (such as ethanol with a concentration of 90%) and extract the pepper raw material powder by low-temperature percolation. The amount of the alcohol solvent used is limited to the point where the pepper raw material is extracted until there is no spiciness (in the examples of the present invention, the amount used is 8 times the mass of the raw material, volume-mass ratio). Collect the percolate used, and concentrate it under reduced pressure (such as a vacuum degree of -0.09 Mpa and a temperature of 55°C) until no alcohol distills out. Let it stand and cool naturally. After the concentrate naturally separates into layers and caking (the alcohol extract with a high piperine content will coagulate into a relatively hard block), remove the clear water to obtain the crude alcohol-extracted pepper oleoresin, that is, the crude pepper oleoresin (in the examples of the present invention, the yield is 10%-12% of the weight of the pepper raw material, and the piperine content of the resin is 35%-40%).

[0037] It should be noted that the above-mentioned crude pepper oleoresin can be the alcohol-extracted pepper oleoresin obtained by the above examples, or the crude pepper oleoresin prepared by supercritical extraction in the prior art or directly purchased pepper oleoresin.

[0038] S2. Add a composite solubilizer;

[0039] Weigh a quantitative amount of the alcohol-extracted pepper oleoresin of S1, add a composite solubilizer (also referred to as a solvent later) prepared according to a fixed ratio. The added amount is 1.5 times to 3 times the mass of the alcohol-extracted oleoresin. Place it in a sealed tank with stirring and heating. Under the conditions of heating and stirring, make the material temperature reach 132°C. Stop heating, keep stirring for 5 minutes, then stop stirring, and let it stand for 24 hours to make the material cool naturally, and the oil-insoluble components precipitate naturally, and the precipitate adheres to the tank wall and the bottom of the tank.

[0040] Among them, by mass percentage, the composite solubilizer includes 10-20% span, 30-40% glycerol monooleate, and 40-60% isopropyl myristate.

[0041] S3. Post-treatment;

[0042] Separate the solid and liquid of the treated pepper oleoresin above to obtain a clear liquid.

[0043] The precipitate obtained by solid-liquid separation also contains some required substances. In order to improve the yield, filter-press the precipitate. For example, the operation is as follows: transfer the precipitate into a sealed filtration tank. A food-grade silica filtration layer with a thickness of 3-5 cm (the particle size of silica is 60 mesh to 80 mesh) is laid in advance at the bottom of the filtration tank. After sealing, introduce compressed air for filter-pressing until no liquid flows out. The obtained filtrate is mixed evenly with the supernatant to obtain a stable liquid and non-crystalline oil-soluble pepper oleoresin.

[0044] After the piperine content of the pepper oleoresin is detected, it can be diluted with various edible oils to prepare standardized pepper oil and essence products, and it is stable for a long time.

[0045] The features and performance of the present invention will be further described in detail below in conjunction with the embodiments.

[0046] Example 1

[0047] An embodiment of the present invention provides a preparation method of a liquid, non-crystalline, oil-soluble piperine oleoresin, including:

[0048] Take 1000 kg of pepper raw materials (piperine content 4.1%), crush them and load them into a percolation tank, percolate and extract at room temperature with 90% ethanol until the percolate is detected to contain almost no piperine (content below 0.05%) (the piperine in the raw material residue is detected to be below 0.1%). Collect the percolate, filter it, and then concentrate it under reduced pressure until no solvent distills out. Let it stand overnight, centrifuge to separate the clear water, and obtain 100 kg of ethanol-extracted piperine oleoresin with a piperine content of 40%.

[0049] Place the ethanol-extracted oleoresin in a closed, stirred, heated mixing tank, add 200 kg of a solvent (composition: 15% span 80, 35% glycerol monooleate, 50% isopropyl myristate). Heat it to a material temperature of 132 °C under stirring conditions, stop heating, continue stirring for 5 minutes, transfer it to a settling tank, and let it stand for 24 hours. Drain the supernatant, transfer the bottom precipitate to a pressure filtration tank, lay a 4-cm-thick food-grade silica gel filter layer, and filter it with compressed air until no liquid flows out. Combine the filtrate and the supernatant, mix them evenly, and obtain 283 kg of liquid, oil-soluble piperine oleoresin with a piperine content of 14%. The filter cake after pressure filtration is 15.8 kg with a piperine content of 1.4%. Among them, for the determination of the piperine content, refer to the high-performance liquid chromatography method for the determination of piperine content in GB / T 17528-2009.

[0050] It should be noted that the glycerol monooleate, span 80, and isopropyl myristate provided in the embodiments of the present invention are all products that can be purchased on the market. For example, glycerol monooleate is purchased from Liaoning Kehai Food Chemical Engineering Co., Ltd., and span 80 is purchased from Guangdong Huana Chemical Co., Ltd., etc.

[0051] Examples 2-6

[0052] Examples 2-6 refer to the preparation method provided in Example 1 to prepare a liquid, non-crystalline, oil-soluble piperine oleoresin, the difference being that the composition of the solvent used is different or the amount of the solvent used is different, specifically as follows:

[0053] Example 2: The solvent composition is 20% span 80, 35% glycerol monooleate, and 45% isopropyl myristate.

[0054] Example 3: The solvent composition is 10% span 40, 40% glycerol monooleate, and 50% isopropyl myristate.

[0055] Example 4: The solvent composition is 13% Span 60, 30% glycerol monooleate, and 57% isopropyl myristate.

[0056] Example 5: The dosage of the solvent is 3 times the mass of the crude piperine oleoresin.

[0057] Example 6: The dosage of the solvent is 1.5 times the mass of the crude piperine oleoresin.

[0058] Process Optimization Research

[0059] 1. Selection of Isopropyl Myristate

[0060] Aiming to obtain a liquid piperine oleoresin and extract piperine from the ethanol-extracted piperine oleoresin as much as possible, different solvents were selected for comparative experiments. Among them, the solvents were selected from edible oils, spices and flavor adjuvants permitted by GB2760. The specific dosages and results are shown in Table 1.

[0061] Table 1

[0062]

[0063]

[0064] As can be seen from the above table, when directly treating the ethanol-extracted piperine oleoresin with edible oils and oil-soluble spices, the dissolution is not complete. None of the edible oils can well extract the flavor substance of pepper - piperine. However, relatively speaking, isopropyl myristate (a spice permitted by GB2760) shows the best performance. Therefore, it was selected as one of the components for dissolving the ethanol-extracted piperine oleoresin.

[0065] 2. Selection of Span

[0066] A total of 5% of the selected emulsifier was mixed into isopropyl myristate as the solvent, and the fixed addition amount of the solvent was 2 times (the mass ratio to the crude piperine oleoresin). It was heated to 132 °C and stirred for 5 minutes, then allowed to stand and settle naturally. The type of emulsifier was determined according to the effect of dissolving the ethanol-extracted piperine oleoresin (the mass of the precipitate and the amount of residual piperine). The emulsifier was required to be selected from varieties that meet GB2760 and GB30616. The crude piperine oleoresin used was the ethanol-extracted piperine oleoresin provided in Example 1, with a mass of 100 kg, a piperine content of 40%, and the mass of the input solvent was 200 kg. The results are shown in Table 2.

[0067] Table 2

[0068]

[0069] As can be seen from the above table, monoglyceride emulsifiers will change the product state, resulting in difficulty in layering, so they are not selected; phospholipid emulsifiers are not very helpful for the solubility of alcohol-extracted pepper oleoresin in solvents; in comparison, Span 80 has obvious effects, so Span 80 is selected as the emulsifier to increase the dissolution effect of the solvent.

[0070] 3. Confirmation of the dosage of Span 80

[0071] Change the mass percentage of Span 80 in the solvent, and investigate the appropriate dosage of Span 80. The process is the same as that in Example 1. There is 100 kg of alcohol-extracted pepper oleoresin with a piperine content of 40%, and the mass of the input solvent is 200 kg. Taking the final product state and piperine content as the investigation indexes, see Table 3.

[0072] Table 3

[0073]

[0074] As can be seen from the above table, increasing the usage amount of Span 80 in the solvent can effectively improve the solubility of the alcohol-extracted oleoresin in the solvent and greatly improve the extraction effect of the solvent on piperine. However, when the usage amount is too large, it will cause difficulty in precipitation separation, and the addition ratio of 15% is the appropriate dosage.

[0075] It should be noted that although the product is in a paste state and the layering effect is poor when 20% Span 80 is selected in the embodiment of the present invention, the reason is that 2 times the amount of solvent is used in this embodiment. When the solvent usage amount continues to increase (such as increasing to 3 times, 4 times, etc.), separation can also be achieved when the addition ratio of Span 80 is increased to 20%. It is not the best scheme with a small solvent usage amount and good effect, but it is still a better scheme.

[0076] 4. Selection of glyceryl monooleate

[0077] The crude pepper oleoresin is treated with a solvent containing 15% Span 80 and 85% isopropyl myristate to obtain a liquid pepper oleoresin. The stability of this liquid pepper oil is observed after standing at room temperature. It is found that crystallization will precipitate in about 7 days. Through the accelerated test of storing in a refrigerator (3 - 5°C), it is found that a small amount of crystallization will appear in the sample within 2 days, and more crystalline substances will precipitate after more than 10 days (up to 8% - 10% of the weight of the oleoresin product). Therefore, an emulsifier needs to be selected to increase the stability of this oleoresin. Specifically as follows:

[0078] Uniformly mix 5% of the selected emulsifier as a stabilizer (replacing 5% of isopropyl myristate) in the solvent (15% Span 80, 85% isopropyl myristate), 100 kg of ethanol-extracted oleoresin pepper, with a piperine content of 40%. The mass of the solvent input is 200 kg. Heat to 132 °C and stir for 5 minutes, then let it stand and settle naturally. Determine the type of emulsifier according to the state of the obtained oleoresin, the extraction effect of piperine, and the stable time of the oleoresin placed in the refrigerator (the emulsifier should be selected from varieties that comply with GB2760 and GB30616). The results are shown in Table 4.

[0079] Table 4

[0080]

[0081] As can be seen from the above table, glycerol monoleate has the effect of increasing the stability of liquid oleoresin pepper.

[0082] 5. Selection of the dosage of glycerol monoleate

[0083] In the uniform solvent (15% Span 80, 85% isopropyl myristate), mix glycerol monoleate in different proportions to replace isopropyl myristate in the same proportion. 100 kg of ethanol-extracted oleoresin pepper, with a piperine content of 40%. The mass of the solvent input is 200 kg. Heat to 132 °C and stir for 5 minutes, then let it stand and settle naturally. Determine the dosage of glycerol monoleate according to the state of the obtained oleoresin, the extraction effect of piperine, and the number of days without crystal precipitation at room temperature. See Table 5.

[0084] Table 5

[0085]

[0086] As can be seen from the above table, when the addition amount of glycerol monoleate is 35%, the state of the obtained liquid oil-soluble oleoresin pepper can be ensured to be stable. More addition will cause the solubility of the solvent in the ethanol-extracted oleoresin pepper to decrease. Therefore, 35% glycerol monoleate is the appropriate proportion.

[0087] It should be noted that although the 30% glycerol monoleate recorded in this example becomes turbid, only a small amount of solid precipitates, and it still meets the usage requirements and can be used. At the same time, since the dosage of glycerol monoleate in the example of the present invention uses twice the amount of solvent, when the amount of solvent is increased further (such as increased to 3 times, 4 times, etc.), the state can also be ensured to be stable when the addition ratio of glycerol monoleate is below 30%. However, the concentration of flavor substances in the oleoresin pepper will decrease slightly. It is not the best solution with a small amount of solvent and good effect, but it is still a relatively good solution.

[0088] 6. Selection of the amount of solvent

[0089] The present invention further verifies the amount of solvent used. The composition of the solvent is: Span 80: 15%, glycerol monooleate: 35%, isopropyl myristate: 50%. The crude piperine oleoresin used is: 100 kg of ethanol-extracted piperine oleoresin with a piperine content of 40%. The results are shown in Table 6.

[0090] Table 6

[0091]

[0092] It can be seen that 2 times the amount of solvent is the appropriate amount. If the amount is lower than this, the dissolution effect of the ethanol-extracted oleoresin is poor. If the amount is higher than this, no better dissolution effect will be obtained, and the content of flavor substances in the finished product will be reduced, and the cost will be increased.

[0093] In summary, the solvent, i.e., the composite solubilizer, used in the embodiment of the present invention can effectively remove the components insoluble in oil in the crude piperine oleoresin, and fully retain the main flavor components of pepper, so that the obtained piperine oleoresin remains in a stable liquid state, the piperine in the piperine oleoresin is not easily precipitated, and it has good oil solubility.

[0094] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A composite solubilizer, characterized in that, The composite solubilizer is used for preparing a liquid crystalline-free oil-soluble oleoresin piperis. By mass percentage, it is composed of 10-20% Span 80, 30-40% glycerol monooleate, and 40-60% isopropyl myristate.

2. The composite solubilizer according to claim 1, wherein By mass percentage, it includes 15% Span 80, 35% glycerol monooleate, and 50% isopropyl myristate.

3. A liquid, non-crystalline, oil-soluble oleoresin of pepper, characterized in that, Its raw materials include a crude oleoresin piperis and the composite solubilizer described in Claim 1 or 2.

4. The oleoresin piperis of claim 3, wherein the oleoresin piperis is a liquid, non-crystalline and oil-soluble, The dosage of the composite solubilizer is 1.5-3 times the mass of the crude oleoresin piperis.

5. The oleoresin of capsicum in liquid non-crystalline oil-soluble form according to claim 3, characterized in that, The dosage of the composite solubilizer is 2 times the mass of the crude oleoresin piperis.

6. The liquid crystalline oil-soluble piperine oleoresin according to any one of claims 3-5, characterized in that, The crude oleoresin piperis is an alcohol-extracted oleoresin piperis.

7. The liquid crystalline oil-soluble oleoresin piperine according to any one of claims 3-5, characterized in that, The liquid crystalline-free oil-soluble oleoresin piperis is a liquid oleoresin piperis without solid precipitation after standing at room temperature for 360 days.

8. A preparation method of the liquid and non-crystalline oil-soluble oleoresin piperis as defined in claim 3, characterized in that, It includes: Processing the crude oleoresin piperis with the composite solubilizer described in Claim 1 or 2.

9. The preparation method according to claim 8, wherein It includes: Mixing the crude oleoresin piperis and the composite solubilizer and then heating, followed by cooling to precipitate oil-insoluble substances, and then performing solid-liquid separation.

10. The preparation method according to claim 9, characterized in that, The heating temperature is 131-140 °C, and the time is 5-10 minutes.

11. The preparation method according to claim 9, wherein The cooling is natural cooling; The natural cooling time is 24-36 hours.

12. The preparation method according to claim 9, wherein, Performing pressure filtration on the precipitate obtained by solid-liquid separation to form a pressure filtrate, and mixing the pressure filtrate with the supernatant obtained by solid-liquid separation; The pressure filtration is carried out in a sealed environment using food-grade silica as the pressure filtration layer.

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