Blueberry pomace coloring agent with aroma enhancement function, preparation method of blueberry pomace coloring agent and application of blueberry pomace coloring agent to cigarette paper

Abstract

The invention discloses a blueberry pomace coloring agent with an aroma enhancement function, a preparation method of the blueberry pomace coloring agent and application of cigarette paper, and belongs to the technical field of cigarette additives. The preparation method takes blueberry processing pomace as a raw material, and sequentially comprises the following steps: washing with ethanol with a specific concentration to remove impurities, carrying out ultrasonic synergistic extraction on pigments and flavor substances by adopting an acid-containing ethanol solution, carrying out two-step specific elution by adopting macroporous adsorption resin to enrich target functional components, and finally concentrating and drying to obtain the coloring agent. The color value of the coloring agent prepared by the method is not less than 50, after the coloring agent is applied to cigarette paper, the cigarette paper can be endowed with stable purple and fresh blueberry fruity flavor at the same time, and the fruity flavor prominence degree in sensory evaluation is improved by not less than 10%. According to the method, high-value utilization of the waste pomace is achieved, the limitation that only color retaining and impurity reducing can be achieved in a traditional process is broken through, and an innovative approach is provided for developing high-end characteristic cigarette products.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of cigarette additives, and particularly relates to a blueberry pomace dyeing agent with flavoring function and a preparation method thereof and application of the blueberry pomace dyeing agent to cigarette paper. BACKGROUND

[0002] In the differentiation design of cigarette products, the function of cigarette paper has exceeded the traditional basic wrapping and become an important carrier for adjusting the sensory experience. Among them, developing purple cigarette paper with elegant color and natural source is an explicit trend to improve the appearance recognition and value of the product, which is usually achieved by applying anthocyanins derived from plants.

[0003] At present, the general technical path for applying natural pigments to cigarette paper focuses on solving the basic application problem, that is, through the extraction and purification process, the pigment purity and color value are obtained to ensure the dyeing effect, and at the same time, the impurities in the raw materials are removed as much as possible to reduce the possible adverse odor during combustion. However, this paradigm with the core of color preservation and impurity reduction has inherent functional limitations: the process design is usually guided by a single physicochemical index, and in the extraction and purification process, flavor substances coexisting with pigments in the raw materials, which may impart pleasant aroma characteristics, are often removed as impurities. Therefore, the natural purple pigment prepared by the existing technology is usually limited to dyeing, and it is difficult to impart a specific purple color to cigarette paper while further bringing additional and coordinated sensory gains.

[0004] On the other hand, from the perspective of high-value utilization of resources, many agricultural product processing by-products (such as pomace, peel) rich in pigments such as anthocyanins have not been fully developed. Such raw materials are complex in composition, not only rich in pigments, but also rich in potential flavor substances such as polyphenols and organic acids, but also accompanied by a large amount of components such as sugars and pectin that may interfere with the combustion quality. If the above general process with the goal of preserving color and reducing impurities is directly applied, it is easy to fall into a dilemma: too many impurities are retained in pursuit of pigment yield, or flavor substances are removed together with impurities, resulting in a single function of the product. Therefore, how to design an integrated process that can simultaneously achieve efficient purification of pigments and selective retention of characteristic flavor substances for such complex by-product raw materials, so as to create a new type of additive with both dyeing and flavoring functions, has become a key problem that has not been effectively solved in the existing technology.

[0005] To solve the above problems, the present application is proposed. SUMMARY

[0006] In view of the single function of natural pigment in the prior art cigarette paper, and the difficulty of the existing general process in realizing efficient purification of pigment and reservation of characteristic flavor from plant processing by-products with complex components, the present application aims to provide a blueberry pomace dyeing agent with flavoring function, and a preparation method and cigarette paper application thereof.

[0007] Specifically, the technical problem to be solved by the present application stems from a double challenge: one is how to convert the high-impurity-content waste pomace generated by blueberry processing into a high-value product, realizing resource utilization; the other is how to break through the limitation of the prior art which mainly focuses on color preservation and impurity reduction, not only extracting pigment with high color value and stability, but also selectively preserving the natural fresh fruit aroma components in the raw material, thereby creating a multifunctional additive with "color and aroma homology". Ultimately, the present application aims to successfully apply this additive to cigarette paper, so that it can not only impart stable and elegant purple color to the paper, but also actively inject pleasant and coordinated characteristic fruit aroma into cigarette smoke, completing the technical leap from passive adaptation to active construction of cigarette sensory quality.

[0008] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0009] In a first aspect, the present application provides a preparation method of a blueberry pomace dyeing agent with flavoring function, taking blueberry processing pomace as raw material, which comprises the following steps:

[0010] Step (1), after drying and crushing the blueberry pomace, washing with a first ethanol aqueous solution and solid-liquid separation, obtaining a solid material;

[0011] Step (2), extracting the solid material with a second ethanol aqueous solution containing acid, and obtaining a crude extract after solid-liquid separation;

[0012] Step (3), loading the crude extract onto a macroporous adsorption resin column, first eluting with a third ethanol aqueous solution and discarding the eluate, then eluting with a fourth ethanol aqueous solution, and collecting the target eluate;

[0013] Step (4), concentrating and drying the target eluate to prepare the dyeing agent.

[0014] Preferably, in step (1), the volume concentration of the first ethanol aqueous solution is 20%-40%, the washing temperature is 20-40℃, and the washing time is 10-30 minutes.

[0015] Preferably, in step (2), the second ethanol aqueous solution containing acid is an ethanol aqueous solution with a volume concentration of 60%-80% containing 0.1%-1.0% (v / v) citric acid or tartaric acid.

[0016] Preferably, in step (2), the extraction is ultrasonic-assisted extraction, the extraction temperature is 40-60 DEG C, the extraction times is 2-3 times, and the extraction time of each time is 30-60 minutes.

[0017] Preferably, in step (3), the macroporous adsorption resin is AB-8 type; the volume concentration of the third ethanol aqueous solution is 20%-30%; and the volume concentration of the fourth ethanol aqueous solution is 65%-75%.

[0018] Preferably, in step (4), before concentration, a metal ion chelating agent is added to the target eluent; the metal ion chelating agent is sodium phytate or sodium citrate, and the addition amount is 0.05%-0.3% of the mass of the target eluent.

[0019] In the second aspect, the present application provides a dyeing agent prepared by the preparation method in the first aspect, characterized in that the color value of the aqueous solution of the dyeing agent at a wavelength of 520 nm is not less than 50.

[0020] In the third aspect, the present application provides a dyed cigarette paper, which is dyed by using the dyeing agent in the second aspect.

[0021] Preferably, in the dyeing process, the dyeing agent is used in combination with a natural mordant; and the natural mordant is acid papaya extract.

[0022] In the fourth aspect, the present application provides a cigarette, which is rolled by using the dyed cigarette paper in the third aspect; and in the sensory evaluation of the cigarette, the index score of fruitiness highlighting degree is increased by not less than 10% compared with a control cigarette using an undyed cigarette paper.

[0023] The present application has the following beneficial effects:

[0024] 1. The present application discards the conventional, relatively single blueberry dry flower or fresh fruit, and creatively selects the waste pomace after blueberry processing as the raw material. This selection is not only based on the consideration of reducing cost and recycling resources, but also based on the deep understanding of the composition of the raw material: the pomace is rich in pigments that can provide color and flavor substances that can contribute to aroma, but also inevitably contains a large amount of impurities such as sugars and pectin. This makes the raw material form a complex system with high coexistence of effective components and interfering impurities, which has the defects of difficult to overcome combustion of mixed gas and unstable product when directly used. The present application successfully solves the problem of simultaneous realization of efficient purification of pigments, deep removal of impurities and selective retention of characteristic flavors from the high-defect raw material through a series of subsequent synergistic processes, and converts it into a high-value functional dyeing agent, realizing the non-obvious technical leap from waste by-product to high-end cigarette additive.

[0025] 2. The various process steps of this invention are not isolated but constitute a whole with strong internal logic and synergistic effects. First, washing with ethanol of a specific concentration removes most of the soluble sugars and other impurities from the fruit pomace at the source, laying a pure foundation for subsequent steps. Second, the combination of an acidic ethanol system and ultrasound-assisted extraction achieves simultaneous extraction of color and aroma while stabilizing pigments. Furthermore, the innovative two-step resin elution strategy, based on the polarity characteristics of the target color-producing and aroma-enhancing components, achieves synergistic enrichment and deep removal of residual impurities. Finally, the introduction of a trace chelating agent solves the problem of storage stability of anthocyanin products. These steps are interconnected and synergistically resolve the technical contradictions of traditional single processes that are inadequate in handling such complex raw materials.

[0026] 3. Through the aforementioned synergistic process, this invention achieves a dual functional breakthrough that traditional "color preservation and impurity reduction" approaches cannot accomplish. The resulting dye not only has a stable color value of no less than 50, meeting the requirements for cigarette paper dyeing, but also significantly improves the smoking experience of cigarettes. When applied to cigarette paper, it actively imparts a clear and pleasant fruity aroma to cigarettes, with a significant improvement (no less than 10%) in the fruit aroma prominence index score compared to the blank control in sensory evaluation. This stable and measurable fruit aroma enhancement effect proves that the technical solution of this invention not only optimizes the physicochemical properties of the product, but also achieves a substantial improvement in the sensory quality of cigarettes, surpassing the limitations of traditional processes that only focus on the purity and stability of the pigment itself. Attached Figure Description

[0027] Figure 1 This is a photograph of a cigarette made using the dyed cigarette paper of this invention.

[0028] Figure 2 for Figure 1 The diagram shows the state of a cigarette during the combustion process. Detailed Implementation

[0029] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the accompanying drawings and embodiments are not intended to limit the technical solutions of the present invention.

[0030] Example 1

[0031] This embodiment provides a method for preparing a blueberry pomace dye that also enhances aroma, comprising the following steps:

[0032] Step (1), the fresh wet residue after blueberry juice extraction was spread on a tray and placed in a 55℃ oven for ventilation and drying for 6-8 hours. Then the material was transferred to a dryer and cooled to room temperature, and weighed. The above drying operation was repeated until the mass difference between two adjacent weighings was not more than 0.5%, which was considered to reach a constant mass. The material was crushed with a crusher and passed through a 40-mesh sieve to obtain blueberry residue dry powder. 100.0 g of the dry powder was accurately weighed and placed in a 2L beaker.

[0033] Step (2), 1500 mL of 30% (v / v) ethanol aqueous solution (first ethanol aqueous solution) was added to the beaker, and mechanical stirring was carried out in a 35℃ constant temperature water bath for 20 minutes. Then, the solid-liquid was separated by suction filtration with a Buchner funnel. The filter cake was quickly washed once with 200 mL of deionized water, and then drained to obtain the deglycosylated pretreated solid material.

[0034] Step (3), the above solid material was transferred to a 2L conical flask, and 1000 mL of 70% ethanol aqueous solution containing 0.5% (v / v) citric acid (second ethanol aqueous solution) was added. The conical flask was placed in an ultrasonic extractor and ultrasonic-assisted extraction was carried out at 50℃ (power 300W) for 50 minutes. After the extraction was completed, the solution was cooled and filtered with filter paper to collect the filtrate. The filter residue was added with 800 mL of the same extraction solution, and the above extraction was repeated once. The two filtrates were combined to obtain the crude extract.

[0035] Step (4), the crude extract was concentrated to no alcohol smell by rotary evaporation at 50℃ and -0.09 MPa. Deionized water was added to make up to 200 mL, and then shaken to obtain the liquid to be purified.

[0036] Step (5), 150 g of AB-8 macroporous adsorption resin (wet state) was weighed, and then soaked in 95% ethanol for 12 hours to fully swell. After washing with deionized water until no alcohol smell was detected, the wet method was used to pack into a glass chromatography column (Φ50 mm×H500 mm) with a column bed volume of about 500 mL.

[0037] 200 mL of the liquid to be purified was loaded onto the resin column at a flow rate of 2 BV / h.

[0038] Step (6), after the loading was completed, 25% ethanol aqueous solution (third ethanol aqueous solution) was used to elute at a flow rate of 3 BV / h, and the eluate of the first 3 column volumes (about 1500 mL) was discarded.

[0039] Then, 70% ethanol aqueous solution (fourth ethanol aqueous solution) was used to continue elution at the same flow rate. The deep purple eluate of this section was collected, about 4 column volumes (about 2000 mL), to obtain the target eluate.

[0040] To the above target eluate, 0.1% (w / w) sodium phytate was added and stirred until completely dissolved. Then, it was concentrated to a thick paste at 45°C under reduced pressure, transferred to a freeze-drying tray and vacuum freeze-dried (-50°C, 24h). The dried product was ground and passed through a 100-mesh sieve to obtain a dark purple-red powder with a blueberry fresh aroma, labeled as Sample A. The yield was calculated as the weight of the dry powder divided by the weight of the dry raw material and multiplied by 100%, and the performance was measured.

[0041] Example 2

[0042] This example is intended to show that, within the parameter range defined in the claims, adjusting the specific values can also implement the present application and achieve the desired effect.

[0043] Step (1), same as Example 1, 100.0 g of blueberry pomace dry powder was weighed.

[0044] Step (2), 1000 mL of 40% (v / v) ethanol aqueous solution was used to wash at 25°C for 30 minutes, and the subsequent solid-liquid separation operation was the same as Example 1.

[0045] Step (3), 1000 mL of 65% ethanol aqueous solution containing 0.2% (v / v) tartaric acid was used for ultrasonic extraction at 45°C for 60 minutes. After the first extraction, the residue was extracted again with 700 mL of the same extraction solution (for 40 minutes). The filtrate was combined;

[0046] Step (4), same as Example 1, concentrated and diluted to 180 mL.

[0047] Step (5), resin pretreatment and column loading, same as Example 1.

[0048] Step (6), loading at a flow rate of 1.5 BV / h (about 750 mL / h). After loading, 20% ethanol aqueous solution was used at the same flow rate for elution, and the first 3.5 column volumes (about 1750 mL) of eluate were discarded. Then, 68% ethanol aqueous solution was used for further elution, and the eluate with a deep purple-red color was collected until the color of the effluent was basically faded, obtaining the target eluate;

[0049] To the target eluate, 0.05% (w / w) sodium citrate was added, dissolved, and then concentrated and vacuum dried (60°C) instead of freeze-drying to obtain a dye powder, labeled as Sample B.

[0050] Comparative Example 1

[0051] Except that the ethanol washing in Step (2) was completely omitted, and 100.0 g of blueberry pomace dry powder was directly subjected to Step (3) extraction, all other steps and parameters were exactly the same as Example 1. The dye was prepared and labeled as Sample D1.

[0052] Comparative Example 2

[0053] In step (6) of Example 1, the two-step elution strategy of low-to-high was cancelled. After the sample was loaded, the elution was directly performed with 70% ethanol aqueous solution at a flow rate of 3 BV / h, and all the colored elution fractions (from the beginning of color to the color basically faded, about 6 column volumes) were collected. The subsequent steps were the same as Example 1. The dyeing agent was prepared, labeled as sample D2.

[0054] Comparative Example 3

[0055] The raw material in Example 1 was replaced with an equal mass (100.0 g) of commercially available dried blueberry flowers, and the ethanol washing step was omitted due to the low sugar content of the dried flowers. The extraction step was directly started, and all subsequent process parameters were consistent with Example 1. The dyeing agent was prepared, labeled as sample D3.

[0056] Comparative Example 4

[0057] In step (7) of Example 1, sodium phytate was not added to the target eluent, and the remaining steps were exactly the same. The dyeing agent was prepared, labeled as sample D4.

[0058] Test Example 1

[0059] Accurately weigh 10.0 mg (accurate to 0.1 mg) of each sample, dissolve in a citric acid-sodium hydrogen phosphate buffer solution with pH = 3.0 and dilute to 100 mL. Using a 1 cm cuvette, the absorbance (A) of each sample at a wavelength of 520 nm was measured on a UV-visible spectrophotometer with the buffer as a blank. The color value (%) was calculated according to the formula color value (%) = A / (C x L), where C is the solution concentration (g / 100 mL) and L is the cuvette thickness (1 cm). The results are shown in Table 1:

[0060] Table 1 Color Value Statistics of Each Sample

[0061] Sample Raw material Key process features Colour value Sample A Blueberry pomace Complete process 68 Sample B Blueberry pomace Parameter adjustment 61 Sample D1 Blueberry pomace No ethanol wash 45 Sample D2 Blueberry pomace Conventional single elution 58 Sample D3 Blueberry dried flowers Change of raw material, no wash 75 Sample D4 Blueberry pomace No addition of sodium phytate 67

[0062] The results show that samples A and B both meet the requirement of color value not less than 50 within the scope of the claims. Comparative Example 1 (D1) has a lot of impurities in the extract due to not being washed, which seriously interferes with the color development of the pigment, resulting in a color value significantly lower than the examples of the present application. Comparative Example 2 (D2) has a low color value than Example 1 because the impurities are not completely separated by using conventional elution. Comparative Example 3 (D3) has the highest color value using dried flower raw materials, but this result only reflects the pigment content, which needs to be combined with sensory evaluation for comprehensive judgment.

[0063] Each sample powder was placed in a weighing bottle and placed open in a constant temperature and humidity chamber at 40°C and 75% relative humidity. Samples were taken on days 0, 7, 14, and 28, and solutions were re-prepared to determine the color value and calculate the color value retention rate. Taking the comparison between sample A (Example 1) and sample D4 (Comparative Example 4) as an example, the results are shown in Table 2.

[0064] Table 2: Accelerated Stability Comparison (Color Value Retention Rate)

[0065] Storage time (days) Sample A (with sodium phytate) Sample D4 (without sodium phytate) 0 100.0 100.0 7 98.5 95.2 14 96.8 89.1 28 94.2 78.5

[0066] The results showed that sample A, which had a trace amount of chelating agent sodium phytate added, had a significantly higher color value retention rate than sample D4, which had no added phytate, after 28 days of accelerated aging. This demonstrates that this stabilization step is crucial for maintaining color stability throughout the product's shelf life.

[0067] Next, this test case also included cigarette application and sensory evaluation, as detailed below:

[0068] 1. Samples A, B, D1, D2, and D3 were prepared into 1% aqueous solutions as dyes using the same method. These solutions were then combined with 1% acid papaya extract mordant and used to dye the same batch of blank cigarette paper using the post-mordant method. The resulting cigarettes were then rolled. A separate group of cigarettes using undyed cigarette paper was set up as a blank control (CK).

[0069] 2. Seven senior cigarette sensory evaluation experts conducted a double-blind evaluation under standard conditions. Following industry methods, they scored the cigarettes on indicators such as fruit aroma prominence, aroma quality, off-flavors, and irritation (fruit aroma prominence is scored out of 10). The results were averaged, with a focus on analyzing the "fruit aroma prominence" score, as shown in Table 3.

[0070] Table 3: Comparison of Sensory Evaluation Scores for Fruit Aroma Prominence

[0071]

[0072] The results showed that cigarettes A and B using the complete process had significantly higher fruit aroma prominence scores than the blank control (an increase of ≥34.5%), and the absolute value increase was more than 2 points, which significantly exceeded the technical effect of an increase of no less than 10% specified in the above instructions, proving that the scheme is reproducible and effective.

[0073] Meanwhile, cigarette D1 (unwashed) scored very low, and tasters generally reported a noticeable burnt smell, proving that ethanol washing is indispensable for removing impurity precursors and ensuring a pure fruity aroma. Cigarette D2 (single-wash) scored significantly lower than cigarette A, demonstrating the key role of two-step specific washing in synergistically enriching color-producing and aroma-enhancing components to obtain a superior aroma.

[0074] In addition, the cigarette D3 using the dry flower raw material has almost the same fruit fragrance score as the blank control, and does not have the characteristic blueberry fruit fragrance at all. This proves that the blueberry pomace is not only a cost selection, but also an irreplaceable functional flavor material source. Compared with the excellent effect of Example 1, the selection of the raw material and the design of the whole process have outstanding substantial features and significant progress.

[0075] The above merely illustrates the specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for preparing a blueberry pomace dye with aroma-enhancing properties, characterized in that, Using blueberry pomace as raw material, the method includes the following steps: Step (1): After drying and crushing the blueberry pomace, wash it with a first ethanol aqueous solution and separate the solid and liquid to obtain solid material; Step (2): Extract the solid material using an acid-containing second ethanol aqueous solution, and obtain a crude extract after solid-liquid separation; Step (3): Load the crude extract onto a macroporous adsorption resin column, first elute with a third ethanol aqueous solution and discard the eluent, then elute with a fourth ethanol aqueous solution and collect the target eluent. Step (4): Concentrate and dry the target eluent to obtain the staining agent.

2. The preparation method according to claim 1, characterized in that, In step (1), the volume concentration of the first ethanol aqueous solution is 20%-40%, the washing temperature is 20-40℃, and the washing time is 10-30 minutes.

3. The preparation method according to claim 1, characterized in that, In step (2), the acid-containing second ethanol aqueous solution is an ethanol aqueous solution containing 0.1%-1.0% (v / v) citric acid or tartaric acid with a volume concentration of 60%-80%.

4. The preparation method according to claim 1, characterized in that, In step (2), the extraction is ultrasound-assisted extraction, the extraction temperature is 40-60℃, the extraction is performed 2-3 times, and the extraction time is 30-60 minutes each time.

5. The preparation method according to claim 1, characterized in that, In step (3), the macroporous adsorption resin is type AB-8; the volume concentration of the third ethanol aqueous solution is 20%-30%; and the volume concentration of the fourth ethanol aqueous solution is 65%-75%.

6. The preparation method according to claim 1, characterized in that, In step (4), before concentration, a metal ion chelating agent is added to the target eluent; the metal ion chelating agent is sodium phytate or sodium citrate, and the amount added is 0.05%-0.3% of the mass of the target eluent.

7. A dye prepared by the method according to any one of claims 1 to 6, characterized in that, The aqueous solution of this dye has a color value of not less than 50 at a wavelength of 520 nm.

8. A dyed cigarette paper, characterized in that, It was dyed using the dyeing agent described in claim 7.

9. The dyed cigarette paper according to claim 8, characterized in that, During the dyeing process, the dye is used in combination with a natural mordant; the natural mordant is an acidic papaya extract.

10. A cigarette, characterized in that, The cigarette is made using the dyed cigarette paper as described in claim 8 or 9; in the sensory evaluation of the cigarette, the fruit aroma prominence score is improved by no less than 10% compared with the control cigarette using undyed cigarette paper.

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