RU2712602C1 - Method of producing lipophilic complexes, polyphenols and food additives from pomegranate juice production by-products - Google Patents

Abstract

FIELD: manufacturing technology.

SUBSTANCE: invention relates to processing of pomegranate juice production by-products. Processing method includes drying of pomegranate juice production by-products, till residual water content is less than 10 wt%, ground, then two-stage extraction is performed. At first step, extraction is carried out in CO₂-extractor at temperature of 75 °C and pressure of 400 bar for 1.5 hours with carbon dioxide with water 1:30 to obtain supercritical CO₂-extract, then 0.5 h mixture of carbon dioxide with ethyl alcohol with water 1:10 to produce wax-paste. Second extraction stage is carried out in a glass reactor with a water-alcohol mixture at temperature of 70 °C for 4 cycles of 30 minutes each at a ratio between the remainder of the raw material from the first extraction step to separate polyphenol-containing extracts therefrom with subsequent separation of alcohol from them, followed by solid-phase extraction of polyphenols, washing of sorbent from foreign impurities and separation of polyphenols bound to sorbent by washing with ethanol, after removal of which polyphenols are obtained in form of dark brown powder. Aqueous part of the extract passed through the sorbent is evaporated under vacuum till dry substances content is equal to 70 wt% to obtain a hydrophilic food flavoring agent; at the same time one performs post-extraction of the after-extracting residue preserving the shape of the fine powder into two fractions with particle size of up to 150 mcm protein-carbohydrate flour and above – insoluble food fibers.

EFFECT: disclosed is a method of producing lipophilic complexes, polyphenols and food additives from pomegranate juice by-products.

1 cl, 4 tbl, 1 dwg

Description

The invention relates to the cosmetic, pharmaceutical and food industries and relates to methods for producing lipophilic complexes and food additives from plant materials, in particular from by-products of the production of pomegranate juice.

The information explosion is a constant increase in the volume of information about the benefits of pomegranate, which began about 25 years ago by the Israeli scientist Ifraim Lanske, which led to the growth of the popularity of this fruit in the European Union, USA, Canada, and other highly developed countries. The popularity of pomegranate juice also increased, which led to a significant increase in its output and a sharp increase in competition in the world markets for this product. Under these conditions, some of the Azerbaijani enterprises producing pomegranate juice were forced to cede their traditional market shares to foreign competitors and even close.

Others, although they survived the market element, as the most popular countermeasures with economic troubles, increase the price of juice from year to year, sometimes even falsify it by mixing with less expensive juices, sugar, etc.

In this situation, some local enterprises considered it necessary to abandon the practice of narrow specialization in the processing of pomegranate and began to conduct their business with the expectation of profit from the sale of not only pomegranate juice, but also other canned food.

And only AZNAR from Geokchay, as befits a specialized leader company, is trying to find a way out of this situation by increasing its involvement in the processing of juice waste and obtaining value-added products from it. There are already receiving lipophilic SC CO ₂ - extract of seed - lesser volume of waste fractions as well as hydrophilic extract of the second - a much larger volume fraction called "peel" and analyzed proposals known foreign firms to transition to the "green" (neat) processing process.

This is customary everywhere in the post-Soviet space — to search for the technology they need only there, “far beyond the ocean,” or, at worst, in Europe.

But what can they offer them abroad, in addition to the technology for the processing of peel and seeds in two different areas with the production of polyphenolic extract from the peel and oil - from seeds (in the spirit of the resource-intensive and too expensive technology used by the American company STIEBS)? Or, maybe, the factory workers will choose another option, designed to obtain not pomegranate juice, but Pomanox extract (patent holder - NutraIingredients, USA) by grinding and extracting the washed pomegranate fruits?

Both of these options in our understanding are “extreme”, since they are left and right at the greatest distance from our technology option. The first of them is diverse, associated with the need to build completely dissimilar to each other in the hardware and technology design of two production sites, so its place on the very edge, for example, of the left flank. And the second option went too far to the right, as it means releasing the extract in return for the pomegranate juice that we all love. And both of them are irrational, since they lead to the formation of significant quantities of new waste in the form of solid post-extraction residues.

Our technology fully meets the requirements of predictive economy and ecology. For us, the post-extraction residue is not new waste, but another opportunity to expand the range of products with the natural strength of pomegranate.

Based on the expected results from the solution we are proposing at the stage of its commercial implementation, they are so optimistic that the problem that it solves may not seem like a problem at all, but one of the rare opportunities for making big money.

It will be possible to purchase pomegranate peel and their seeds (dried raw materials) at a price of $ 1 / kg; from this 1 kg of raw materials will be obtained in the amount of 0.68 kg with a cost of $ 6.4, which will be sold for $ 25.4 with a profit of $ 19.

World production of pomegranate fruits is now at the level of 2.5-3 million tons per year, of which approximately 25% goes into juice processing. This means that every year the world receives not only 300 thousand tons of juice, but also 350 thousand tons of waste.

Recycling such an amount of waste according to our proposed technology can produce $ 3 billion worth of ingredients.

The scale and social significance of the event under consideration and the successful alignment between costs and revenues (1: 4) suggests that the organization of processing waste products of pomegranate juice in the form in which we propose to do this cannot be considered as an ordinary business event . This is a rare opportunity to find your “golden niche” and immerse yourself in a profitable business not only for the authors of the solution, but also for investors.

But we think so, and we must convince of this to convince the managers who are engaged in the search for innovative developments for private or public funding, who are “sick” for their money. And this will not be an easy task for us, given that for every good argument - “for”, you can bring no less weighty argument - “against”.

But it is necessary to solve this problem, as the time has come to highlight from the diversity of opinions and approaches that valuable that has been achieved over all previous years and take a step forward in solving this problem.

It should be noted that the research and development work of the last few years was carried out in order to study the possibilities for processing pomegranates not only into juice, but also into other products, such as Frozen arils - a product from freezing pomegranate seeds with added 15% sugar syrup , Appertised arils - pomegranate seeds placed in tin cans (with their subsequent sealing and sterilization) in 15% syrup, Arils in vinegar - pomegranate seeds in vinegar (5% acidity) with packaging in glass jars of minimally processed peel, squash, molasses (sold kt boiling mixture consisting of 8 parts of pomegranate juice and 1 part syrup), frozen garnet grains, corn syrup, anardana (pomegranate rind acidic wild sun drying), oil from the seeds of a pomegranate, confectionery and even perfume [Dhinesh K.V. Pomegranate Processing and Value Addition: Review / K.V. Dhinesh, D. Ramasami // J Food Process Technol., 2016. - Volume 7. - Issue 3. - Pp. 1-11. DOI: 10.4172 / 2157-7110.1000565].

But these products have not gained popularity due to the lack of commercially viable technologies for their preparation and demand.

Analysis of the proposed methods for processing the peel and seeds remaining after receiving juice from pomegranate fruits shows that most of them as the main element include grinding and extraction (from Latin extraho - I extract it), i.e. selectively extracting the desired components from them using a suitable solvent.

In raw form, the pomegranate peel and seeds contain, respectively, about 70 and 55% of their total wet weight and are classified as perishable products.

The peel of pomegranate fruit at a temperature of 0 ° C can maintain its quality for 21 days, at 2 ° C - up to 18 days, at 5 ° C - up to 14 days [Seeram N.P. In vitro antiproliferative, apoptotic and antioxidant activities of punicalagin, ellagic acid and a total pomegranate tannin extract are - enhanced in combination with other polyphenols as found in pomegranate juice / N.P. Seeram, L.S. Adams, S.M. Henning, Y. Niu, Y. Zhang, M.G. Nair, D. Heber // Journal of Nutritional Biochemistry, 2005. - Vol. 16 (6). - Pp. 360-367].

The simplest and most effective way to obtain long-term semi-finished products from peel and pomegranate seeds is to dry them to a residual water content below a critical value of 14 wt. %

As a result of drying, the peel and seeds turn into more suitable (concentrated) materials for further transportation and processing by extraction at any place and at any time suitable for this.

In a dried peel, the concentration of water-soluble polyphenols is approximately 3 times that in a raw peel. In dried seeds, the content of fat, protein, starch and other substances is 2 times higher than in raw seeds. Therefore, most of the known methods involve the use of raw peel rather than raw peel.

As for the list of target products that can be obtained by extraction of dried peel and seeds, it completely depends on the characteristics of their chemical composition.

There are two unique substances in pomegranates, in terms of the benefits they bring to human health: punicalagins (punicalagins, extremely powerful antioxidants of a polyphenolic nature found in pomegranate juice and peel) and punicic acid (punicic acid), presented in pomegranate seed oil; It is a type of conjugated linoleic acid with a strong biological effect.

While the peel is a highly rich source of polyphenols, monosaccharides, organic acids and minerals, seeds are exceptionally rich in protein, starch and storage lipids.

Due to the high content of biologically active ellagitannins, alkaloids, aromatic compounds (coumarin glycosides), enzymes, pomegranate peel has commercial value as an additive to food and animal feed. Pressed seeds are rich in fatty acids and sterols [Seeram N.P. In vitro antiproliferative, apoptotic and antioxidant activities of punicalagin, ellagic acid and a total pomegranate tannin extract are - enhanced in combination with other polyphenols as found in pomegranate juice / N.P. Seeram, L.S. Adams, S.M. Henning, Y. Niu, Y. Zhang, M.G. Nair, D. Heber // Journal of Nutritional Biochemistry, 2005. - Vol. 16 (6). - Pp. 360-367].

These differences in the chemical composition of the peel and seeds are so obvious that most researchers make plans to create two completely different technologies for their processing. Since these technologies are different, their implementation also requires the creation of completely different independent sections in terms of hardware design - one for processing the peel, the other for processing the seeds. But the peel and seeds must still be dried, creating for this purpose also a drying area.

The multifaceted nature of this typical scheme could not change as a result of its small adjustment: some authors used separation membranes to isolate polyphenols from extracts, others - polymer resins; some received a lipid complex from seeds by pressing them in the press, others - by extraction methods, including extraction by fluids.

She only showed that the list of processed products of peel and pomegranate seeds can be very wide. These can be supplements in phenol-rich diets and cosmetics, supplements to increase the shelf life of foods, functional ingredients to improve food quality and promote human health, unicellular proteins, industrial enzymes, and many others.

At the same time, out of hundreds of enterprises engaged in the processing of pomegranates into juice in different parts of the world, almost one does not want to undertake to develop these new industries. Although everyone understands that the peel and pressed seeds are extremely promising raw materials due to the costs already incurred.

But what could be the general disadvantage of the known methods? One that prevents their introduction into production?

To make it easier to answer this question, we put it in a slightly different form: what do pomegranate processors dislike in their business more than anything else?

The answer suggests itself: of course, they would not want to engage in the disposal of juice waste in a landfill, given that a lot of this waste is generated.

In this regard, the main attention should be paid to deepening the processing process, taking into account previous omissions. It should be conducted with a more informed access to the metabolic properties of pomegranate and manufactured products in different conditions in order to develop a database that will create opportunities for the successful application of the created technology. In the long term, this should be a European-level processing technology for pomegranates to produce not only juice, but also products with added value - medicinal extracts, powder and other products, the cost of which would not include the costs of the purchase and delivery of fresh pomegranate fruits.

In fact, when analyzing well-known solutions, the conversation is all the time about technologies built on the same approach. Any of them can be described as “high-waste technology” or, at best, as “low-waste technology”. And none of these well-known technologies can be classified as non-waste technology.

In the classical standard scheme, the processing of pomegranates does not go beyond the scope of the process aimed at obtaining pomegranate juice of cold pressing and its direct bottling or concentration for the purpose of recovery and bottling at a later date. The term "multi-waste" is applicable to it.

In relation to several technologies closest to our invention, the term “low-waste” can be used, which is most often used to refer to a process that allows reducing solid waste production to the technically possible minimum and implying that the process is close to a closed cycle. But they leave behind waste, only in a new form, such as post-extraction residues, which innovation managers cannot help but pay attention to, when deciding on the introduction of a new scheme, they simply must rely on predictive savings.

We want to ensure that the technology of processing pomegranates has changed so that, in terms of effectiveness, it fits the term “waste-free”, which is used in the literature to refer to a technological process that ensures the receipt of a finished product or part of it with small or completely recyclable waste. At least “with a stretch”, since “waste-free technology” is the principle of organization of production, which implies the use of not only raw materials, but also energy in a closed cycle.

Even in the most progressive known methods (which we will continue to call methods-analogues), the processes of processing the peel and seeds of pomegranate are constructed in such a way that with their help it would be possible to produce 1-2 products with a fixed capacity.

But how can one be content with this at a time when sharply increased competition in the world market of pomegranate juice, as well as resource-saving requirements, make the task of creating workable multi-productive production plants of a continuous type urgent, the main stage of which is a flexible system for gradually deepening the processing process?

It is precisely because of insufficient full compliance with the dynamic nature of the market economy and its growing requirements all the time that not one of the completed developments concerning the processing of waste products from pomegranate juice produced the expected furor.

The world gives way to someone who knows where he is going. © Ralph Waldo Emerson.

The beginning of creating a new technology should be an idea, let's call it an idea. But it must be a real plan.

Our plan is mainly based on the fact that when creating a new scheme for processing peel and pomegranate seeds, one should be guided by the principle of technological consolidation within all the main resource-intensive operations and processes that should become elements of one general scheme for joint processing of peel and seeds.

In other words, we must abandon the traditional approach practiced by everyone (including for research purposes), according to which the pomegranate peel and their seeds (dried raw materials) are assessed as two completely different and incompatible in terms of joint processing of types of secondary raw materials.

The combination of the processing of dried peel and dried seeds in one technology is a blessing that will give many advantages, such as a significant reduction in the cost of organizing their processing. Indeed, in this case, it will be necessary to create only one site for their processing, instead of two, on which it will be possible to produce products in a larger volume and in a wider range.

But achieving this requires an answer to one global question: where should one begin to implement this idea?

Well, of course, we must begin this business by mixing the peel and seeds (which before this must still be dried and crushed).

This is an incredibly successful find, taking into account the fact that almost all polyphenols are contained in the peel, and it is mixed with seeds in which polyphenols are practically absent, but there is a lot of protein and starch. This means that the processing facility will initially contain less polyphenols and more protein and starch than a single peel. And this, in turn, will facilitate the further task of bringing the residual polyphenol content in the post-extraction residue to a low level acceptable for the energy product. And this will be a very important achievement, because, along with a decrease in the content in the post-extraction residue of the mass fraction of polyphenols, the content of protein and starch in it will noticeably increase, which cannot but affect its good quality and will help to further its processing as a source of protein and carbohydrates.

Such a highly rationalistic approach was implemented by us in a new model scheme.

Along with the new that distinguishes it from the well-known schemes, it has incorporated some elements that were already used in some well-known methods with the difference that we used them in the joint processing of peel and seeds or pulp of fruits, and in the known methods they were used for separate processing peel or seed.

Given this, some of these well-known were chosen by us as analogues of the invention.

One of them is the method according to US patent No. 7897791 [1]. It includes the extraction of ellagitannins from pomegranate peel with water or methanol, separation of the resulting extracts and their processing by solid-phase extraction aimed at retaining polyphenols with a solid polymer adsorbent, followed by removal of ballast substances from the surface of the adsorbent using the method of liquid vacuum aspiration, elution (washing) of the adsorbent with a solvent ellagitannins and the allocation of ellagitannins in the composition of the solid mixture remaining after complete evaporation of the eluate. This mixture is a nutraceutical composition or a composition that relates to the treatment and prevention of cardiovascular disease.

However, the use of a toxic organic solvent such as methanol for ellagitannin extraction should be limited to substitution with other solvents.

The use of water for this purpose in this case is also impractical, since water extracts a lot of “ballast substances” from raw materials — soluble pectin, other biocolloids that cause clouding of the separated extracts. It is necessary to process the separated extracts with enzymes to eliminate colloidal turbidity, which leads to a rise in price and complexity of the technology, as well as to an increase in the time required for its implementation.

Another disadvantage of this method is that it is designed for processing peels and does not cover another part of the waste products of pomegranate juice - squeezed seeds. Moreover, even that part of the waste with the name “peel” to which it applies is not fully used and the method leaves behind new waste in the form of a solid post-extraction residue.

Another method that we have chosen as an analogue of the invention in terms of processing the peel [2], differs in that it is aimed at obtaining not natural ellagitanins, but the product of their acid hydrolysis - ellagic acid. The method involves the extraction of ellagitanins, followed by their acid hydrolysis and selective extraction of ellagic acid by extraction with methanol and recrystallization.

The advantages of this analogue method include the fact that it provides a rather high yield of ellagic acid of 90% purity in an amount of about 3.5 kg per 100 kg of pomegranate peel when using reagents, many of which are reusable.

However, the method also has a significant drawback, which is that ellagic acid is less bioavailable than punicalagins (from the previous analogue method).

In addition, this method has a limited nature of application, as it is designed for processing peel and does not apply to another fraction of the waste - seeds.

Another disadvantage is that the function of the method does not include further processing of the massive post-extraction residue.

Another analogue of the invention in terms of processing the peel can be considered the solution according to RU patent under the number 2034850 C1 [3], which relates to the technology of producing pectin from the peel of pomegranate fruits.

The method includes the following operations: hydrolysis-extraction of raw materials by exposing them to hot water with a temperature of 70-75 ° C; purification of the liquid extract by passing through a mechanical filter; the allocation of pectin from the solution by exposure to the solution of light metal salts; purification of pectin by dehydration with an alcohol solution; drying.

However, this method, with such a lengthy processing process, including hydrolysis-extraction of the peel at an elevated temperature, isolation, purification and drying of pectin, results in the production of pectin alone in the amount of 5% of the dry substance of the peel, which indicates that this method is very far from being rational.

As another common drawback of analogues of the invention in terms of processing the peel, one can also note this.

Not only do they have a limited nature of application and do not apply to seeds, they are also not as effective as methods of processing the peel as it might seem at first glance. After all, they are all designed for the possible complete extraction of only soluble fractions from raw materials and their function does not include the regulation of the processing process, taking into account the influence it exerts on the composition of the post-extraction residue. And such regulation in this case is important and that is why.

After extraction of soluble substances, the insoluble residue contains, of course, a little of them, but at the same time it contains almost 2 times more fat-like substances prone to oxidation (based on the total amount of solids) than the original peel.

With a higher content of fats, their oxidation and rancidity can become more massive, which reduces the quality of the post-extraction residue as a raw material for further processing into powdery products of long-term storage.

Given the importance of the changes in the composition of this type of raw material at certain stages of its processing, when developing our technology, we had to avoid the accumulation of fat-like substances in the post-extraction residue. The best way out of this situation would be to use the fat-like substances of the peel in obtaining an additional lipophilic product. It also has the fact that the pomegranate peel contains structural lipids, which should differ from the storage lipids of their seeds with a higher pharmacological value.

But still, the central innovation in our method should be the preparation of an individual peel and individual seeds of a mixed extraction object.

Schmilovitch, Yoav Sarig, Avraham Daskal et al. Apparatus and method for extracting pomegranate seeds from pomegranates // US 20150082998 A1. 2015]. При машинном разделении гранатов в семенных гнездах «застревают» зерна в количестве около 1% от общей массы сырой кожуры, а в отделенных от кожуры зернах можно найти 3-10% от их полной сырой массы частичек корки, светлых перегородок и семенных гнезд. А это значит, что кожура и отжатые семена поступают на сушку не в «чистом» виде, а в смеси. Кроме того, на некоторых заводах в пресс подают не индивидуальные зерна, а целые плоды - что же тогда говорить о побочном продукте от такой технологии - жоме, в котором кожура и семена находятся вместе изначально?The expediency of the operation to mix the peel and seeds is also indicated by the fact that in practice, therefore, one has to deal with the peel from machine cleaning of pomegranates, to which a certain amount of seeds is mixed. This is due to the fact that the complete separation of pomegranates into peels and grains (succulent seeds) cannot be achieved even using the most modern garnet-cleaning machines [

Schmilovitch, Yoav Sarig, Avraham Daskal et al. Apparatus and method for extracting pomegranate seeds from pomegranates // US 20150082998 A1. 2015]. During machine separation of pomegranates, in the seed nests, grains “get stuck” in an amount of about 1% of the total wet peel mass, and in grains separated from the peel, 3-10% of their total wet mass of crust particles, light partitions, and seed nests can be found. This means that the peel and squeezed seeds are not dried in “pure” form for drying, but in a mixture. In addition, in some plants, the press does not deliver individual grains, but whole fruits - what then can be said about the by-product of this technology - bagasse, in which the peel and seeds are located together initially?

Before proceeding to the description of the essence and disadvantages of the solution closest to the invention in terms of processing pressed seeds, we will try to explain why of the two possible ways: 1 - obtaining oil by pressing; 2-obtaining SC CO ₂ -extract with oil properties, we have chosen the second method.

Press oil of pomegranate seeds is often described as a unique product, but with an “unusual aroma” and a “putrid” or “unpleasant” odor.

Given this, the authors of US patent No. 20150368584 A1 [4] proposed their own method of producing pomegranate oil, devoid of these disadvantages. It includes the stages of separation - separation of seeds from the wort, drying of the seeds, cleaning the dried seeds from pieces of leathery pericarp and internal light fleshy partitions, exfoliation, obtaining oil by extraction or by applying pressure to the crushed seeds, stabilizing the oil, and deodorizing the oil.

However, for all the complexity of this scheme, which involves a rather lengthy processing of raw materials and the oil itself in several stages, and it does not guarantee complete disposal of the product from an unpleasant smell.

The thing is that cold-pressed pomegranate seed oil and pomegranate seed oil from hexane extraction contain lipophilic substances prone to rapid decay (rancidity).

Pomegranate seed oil obtained by known methods not only has an unpleasant odor, but can also form a gel-like substance that makes it difficult to use for various products. Standard extraction and deodorization methods do not increase the stability of the oil, which easily turns into a polymerized product

It is believed that it is precisely the high levels of beneficial components in pomegranate seed oil that make it more reactive compared to other rare oils. Sometimes polymerized pomegranate oil is treated with hexane, trying to return it back to the desired liquid state. However, this standard technique in this case does not give the desired effect.

At the same time, the manufacturing technology of SC СО ₂ - extract from pomegranate seeds is not as multistage and complicated as the above-described technology of oil from pomegranate seeds by the press method, since it does not include the stages of refining, bleaching and deodorization. Yes, and the target product itself - SC СО ₂ - the extract is completely devoid of bad smell and other disadvantages characteristic of press oil. After adding 0.05 wt. % of organic rosemary extract as an antioxidant, SC СО ₂ pomegranate seed extract can be perfectly stored for a year in unopened packaging under cool storage conditions and exclude light.

Comparison of the composition of SC CO ₂ -extract with the composition of the oil obtained by extracting pomegranate seeds with hexane in a Soxhlet apparatus (extractor) did not reveal differences between these products in the composition of fatty acids. The total amount of tocopherols in the oil from seed extraction with supercritical CO ₂ was about 14% higher than in the oil extracted from the seeds in a Soxhlet apparatus [Guangmin Liu. Supercritical CO ₂ optimization of pomegranate (Punica granatum L.) seed oils using response surface methodology / Lui Guangmin, Xu Xiang, Hao Qinfend, Gao Yanxiang // Food science and Technology, 2009. - Vol. 42 ((9). - P. 1491-1495]

Therefore, we took the path of isolating the lipophilic fraction from the seeds of pomegranate not in the form of oil, but in the form of an SC СО ₂ extract with the properties of pomegranate seed oil, and thereby got rid of the need to solve a lot of issues that become unnecessary in this case and disappear themselves by oneself.

The process of supercritical CO ₂ extraction eliminates the need for potentially hazardous solvents such as hexane, and thereby avoids unnecessary pollution and potential harm to humans.

Another positive aspect of the SC CO ₂ extraction process is the aroma characteristic of this type of raw material, but in a more original form. The aroma of SK CO ₂ pomegranate seed extract is more lively and active than that of cold pressed pomegranate seed oil.

Our SC CO ₂ extract is a beautiful, clear yellow oil rich in nutrients, unsaturated fatty acids, plant sterols, tocopherols and squalene. When it is received, environmentally friendly food-grade carbon dioxide is used. Therefore, the extract does not contain soluble residues, inorganic salts and heavy metals - it is only a pure, nutrient-rich oil. Recommended for use in moisturizers and lotions, as part of anti-aging compositions and kits for dry, irritated or chapped skin. Pomegranate seed extract can promote skin regeneration, stimulate self-healing mechanisms, improve skin elasticity and reduce wrinkles. Pomegranate seed oil has calming properties and is therefore useful in skin sedatives. For the extract, such a composition is typical: punic acid 62.5%; isomers of punic acid 14.7%; linoleic acid 9.8%; palmitic acid 3.2%; stearic acid 2.1%; oleic acid 7.7%; tocopherols 0.66%; squalene 0.13%; sterols 0.98%; little-known lipophilic substances 3.6%.

We calculated that people would prefer the foul odor of earth oil, a fresher, greener scent of SC CO ₂ -extract, and chose carbon dioxide extraction under supercritical conditions as the most acceptable method for isolating the lipophilic fraction from pomegranate seeds today.

Now, as we have already promised, we will move on to characterizing (extraction) methods of producing oil from recycled pomegranate raw materials that are closer to the invention.

A known method of producing pomegranate oil [5], including drying the washed seeds of pomegranate, grinding, extraction with methylene chloride for 24-26 hours at 40-45 ° C, followed by distillation of the solvent. The yield of pomegranate oil is 29-30%.

The disadvantage of this method, an analogue with a sufficiently high output of the lipid complex, is the use of a toxic solvent - methylene chloride, the residual amounts of which in the obtained lipid complex require strict regulatory regulation, as well as the use of seeds containing maximum storage lipids and to a lesser extent structural materials, which reduces the alleged pharmacological value.

It is known that oilseed pulp contains, in addition to storage lipids, significant quantities of valuable biologically active substances of border polarity, the extraction of which allows one to obtain promising products for use in the pharmaceutical, perfumery, and food industries.

The closest analogue of the invention in terms of the production of oil and other lipophilic substances is a method for producing a lipid complex from pomegranate pulp [6], which consists in the fact that the pulp dried to a moisture content of not more than 5% is crushed to a particle size of 0.5- 1 mm, extraction is carried out at a ratio of raw materials-extractant 1: 5-1: 10 using gasoline or hexane or chloroform as an extractant for 3 hours, followed by distillation of the extractant and additional extraction of meal with a ratio of raw materials-extractant 1 : 5-1: 10 admixture hexane: isopropanol 3: 1 for 3 hours, followed by distilling off the extractant, and combining the obtained extracts. The output of the lipid complex is 25-28%.

The disadvantage of this method with a sufficiently high yield of storage lipids and biologically active substances of border polarity is the use of solvents that can harm the health of personnel working with them. Another drawback is that its implementation is not associated with the production of pomegranate oil, but a lipid complex with characteristics and texture that are unique to it, which in fact means refusing to receive pomegranate seed oil that has already been loved by the consumer and switching to a mixture consisting of fatty pomegranate seed oil and fat-like peel substances. In addition, the method is characterized by a low utilization rate of dried pulp, as it leads to the formation of new waste in the form of a post-extraction residue in the amount of 72-75% of the initial mass of dried pulp.

The objective of the invention is to combine the processes of extraction of by-products in the form of individual pomegranate peel and their individual seeds in one technology, and not to the detriment of the established practice of selective extraction of related groups of substances (such as storage lipids of seeds and polyphenols of the peel), and in its development, and increasing the purity and depth of the processing process.

The problem is solved in that the method of processing by-products of the production of pomegranate juice to obtain a lipophilic complex, polyphenols and food additives includes drying by-products, grinding and extraction of lipophilic and hydrophilic fractions, characterized in that the by-products are dried to a residual water content of <10 mass .%, the products of their drying are crushed to particles with a size of 1-3 mm, after which the products from drying and grinding of the individual peel and individual seeds are combined together in weight a 7: 3 ratio or use the product of drying and chopping pulp of fruits, which is a mixture already ready for further processing by extraction, with the same balance between the peel and seeds, the extraction is carried out in two stages: the first stage of extraction is carried out in a CO2 extractor with at a temperature of 75 ° C and a pressure of 400 bar, first for 1.5 hours with carbon dioxide at a hydraulic module of 1:30 to obtain a supercritical CO2 extract with the properties of pomegranate seed oil in the first stage, then another 0.5 hours with a mixture containing 99 wt .% carbon dioxide kind and 1 wt.% ethyl alcohol with a concentration of 95 ± 0.2 vol.%, with a hydraulic module of 1:10 to obtain a wax paste with the properties of the fat-like substances of its peel in the second stage, the second extraction stage is carried out in a glass reactor with a water-alcohol mixture with an ethanol concentration of 95 ± 0.2 vol.% at a temperature of 70 ° C in 4 cycles of 30 min each, with a ratio between the remainder of the feed from the 1st extraction stage and a solvent of 1: 4, with the separation of four portions of polyphenol-containing extracts, one at a time servings in each cycle, and sending them as they separate in sleep a separator, where alcohol is distilled off under vacuum to a predetermined dry matter content in the bottom residue, after which the aqueous portion of the extract remaining after alcohol removal is unloaded from the working capacity of the alcohol separator and introduced in parts into the vacuum aspiration column of the solid-phase extraction system, where it passes through the adsorption Amberlite XAD-16 resin, after the target substance is retained by the sorbent, as judged by the color of the extract: first it is dark brown, after holding the polyphenols the resin becomes pale yellow, the sorbent is washed from foreign impurities, for which distilled water is passed through it until the sweet pale yellow eluate becomes transparent, the remaining water is removed from the surface of the resin by vacuum aspiration, and the polyphenols bound to it are washed off with ethanol to obtain dark brown solution, ethanol is removed in a rotary evaporator under vacuum at a low temperature of 37 ° C, obtaining polyphenols in the form of a dark brown powder, and the part of the aqueous extract that passed through the sorbent is evaporated in vacuo to a solids content of 70 wt.% to obtain a hydrophilic food flavor, at the same time, the post-ejection residue, which retains the form of a fine powder, is sieved into two fractions with a particle size of up to 150 μm protein - carbohydrate flour and above - insoluble dietary fiber.

The technical result of the invention is the creation of a workable multi-productive production of a continuous type with a flexible system of gradual deepening of the processing process.

The method is as follows.

In the production of biologically active complexes and food additives, by-products of the production of pomegranate juice in the form of individual peels and individual seeds or in the form of bagasse varieties (or a mixture of pomological varieties) growing in the Republic of Azerbaijan and used to produce juice can be used, as a rule, they can be used. . The pulp is formed in the process of obtaining juice by directly squeezing washed pomegranates of one variety or a mixture of pomological varieties in the press, and peel and seeds are by-products of the technology, which involves squeezing juice from juicy seeds separated from the rest of the fruit.

These by-products in the initial state are perishable plant materials with a relatively high humidity of 60-70%, therefore, the first thing they are dried to obtain secondary pomegranate raw materials in the form of dry semi-finished pulp of fruits or in the form of dry semi-finished products of individual peel of fruits and their individual seeds for long-term storage .

Drying the individual peel and individual seeds or pulp is carried out in an infrared conveyor dryer at a temperature of 130-140 ° C for 15-30 minutes to a residual water content of ≤10%.

Such transient drying allows you to better maintain the original color and labile substances of the products.

The dried by-products are crushed to particles with a size of 3-1 mm.

The optimality of this degree of grinding was established experimentally on the basis of its influence on the yield of extracts. With larger particle sizes than 3-1 mm, the degree of extraction of lipophilic fractions is reduced. In this case, grinding to a finer powder state is impossible for the simple reason that it complicates the process of further extraction of the hydrophilic fraction.

The crushed by-products in the form of an individual peel and individual seeds immediately before their further processing (by the method of continuous extraction) are combined together in a weight ratio of 7: 3 (this does not apply to the product of drying and grinding of pulp of fruits, which is a mixture already ready for further processing by extraction using the mixture , with approximately the same balance between peel and seed).

The extraction is carried out in two stages with the participation of three solvents, given that the extraction object is characterized by a high content of both two groups of lipophilic substances of different solubility and hydrophilic substances.

The first stage of extraction is carried out in a CO ₂ extractor in two stages with a water module (the ratio between the feed and the total amount of solvent used) in the first stage is 1:30, in the second - 1:10

In the first stage, carbon dioxide is used as a solvent, which is fed to the extractor, separator and high-pressure cylinder at the beginning of the working process and the necessary thermodynamic parameters are set in a CO ₂ extractor, in this case, a pressure of 400 MPa and a temperature of 75 ° C. The extraction process at these parameters is carried out for 1.5 hours, after which time the solvent flow is shut off, the pressure in the system is completely relieved by passing the outgoing solvent through the fraction collector (separator), and SK СО ₂ is extracted using the bottom tap; properties of pomegranate seed oil.

Then, the second stage of the 1st stage of extraction is carried out in a CO ₂ extractor, for which a mixture of carbon dioxide and ethyl alcohol is supplied to the extractor, separator and high pressure cylinder (in this case, ethyl alcohol is used in an amount of 1 wt.%, And carbon dioxide is used 99 wt.% Of the total solvent mass) and set the necessary pressure (400 MPa) and temperature (75 ° С) in a СО ₂ - extractor. The extraction process at these parameters is carried out for 0.5 hours, after which time the solvent flow is shut off, the pressure in the system is completely relieved, passing the outgoing solvent through the fraction collector (separator), and the wax paste is removed using a bottom valve.

To both target products from the 1st stage of extraction, before packaging, add 0.005 wt. % rosemary antioxidant extract.

The 2nd extraction stage is carried out in a glass reactor (where the solid residue from the 1st extraction stage is transferred) with a water-alcohol mixture with an ethanol concentration of 95 ± 0.2% vol. at a temperature of 70 ° C in 4 cycles of 30 minutes each with a ratio between the extracted material and the solvent at the beginning of each of these cycles 1: 4.

Each such cycle begins with feeding into the reactor (with a working volume of 100 l) a solvent in an amount of ≈64 l (taking into account that the weight of the feedstock decreased slightly after the 1st extraction step, and the hydraulic module should be equal to 1: 4) and end with separation under the pressure of the resulting extract through the bottom drain valve.

The extracts, as they are separated, are sent to the apparatus for the regeneration of alcohol from natural extracts-alcohol separator (100 l).

In the apparatus, all alcohol is distilled off under vacuum (the end of the process is judged by the specific smell characteristic of alcohol).

As a result of such processing of extracts from all 6 cycles, a dark brown water still residue is formed in a volume of 15-16 l with a content of 43 ± 2% dry matter, unloaded from the working capacity of the evaporator and sent to an automatic solid-phase extraction (TFE) system for processing in a special a column (cartridge) with resin until the resin is completely retained by the polyphenols.

The resin has a surface on which ellagitannins are adsorbed. A preferred class of adsorbent resins are styrene and divinylbenzene polymer crosslinked resins, such as, for example, the AMBERLITE series resins, for example AMBERLITE XAD-16, which are commercially available from Rohm & Haas Co., Philadelphia Pa. Other polymer crosslinked styrene and divinylbenzene adsorbent resins suitable for use in accordance with the invention are XFS-4257, XFS-4022, XUS-40323 and XUS-40322 manufactured by The Dow Chemical Company, Midland, Michigan and the like. However, it is better to use the commercially available crosslinked styrene-divinylbenzene (SDVB) copolymer resin AMBERLITE XAD-16 having a particle size of from 100 to 200 microns. AMBERLITE XAD-16 has a macroreticular structure with a continuous polymer phase and a continuous pore phase.

Other adsorbents of the AMBERLITE XAD series, which contain hydrophobic macroreticular resin granules with particle sizes in the range of 100-200 microns, are also effective in the methods of the present invention. Moreover, various AMBERLITES variants, such as adsorbents of the AMERCHROM CG series with particle sizes in the range of 100-200 microns, may also be suitable for use in the present invention. AMBERLITE XAD-16 is preferred because it can be reused repeatedly (more than 100 times). However, to obtain the products of the present invention, it is important and / or desirable to use resins approved for use by the competent authorities.

Before loading the bottom residue into a vacuum column with XAD-16 adsorption resin, the adsorbent is conditioned by preliminary washing in methanol and keeping it in water for 12 hours

Then the bottom residue in 2 l portions is introduced into a TFE vacuum suction column, where it passes through Amberlite XAD-16 adsorption resin (5 kg).

The purpose of the bottoms loading is to quantitatively retain the target substance on the TFE cartridge, while the matrix impurities are removed.

After the target substance is retained by the sorbent (as judged by the color of the extract: first it is dark brown, after holding the polyphenols with the resin it turns pale yellow), the sorbent is washed from foreign impurities. Why distilled water is passed through it until the sweet pale yellow eluate becomes clear (usually 40 l of water). The remaining water is removed from the resin by vacuum aspiration.

At the final stage, quantitative elution of the target component occurs.

Any solvent may be used to elute ellagitaninins from the adsorbent.

However, it is preferable to use lower alkanols for this purpose, the structural formula of which contains 1 to 4 carbon atoms, and even better ethanol (ethyl alcohol), since it is approved for use in the preparation of food products. It can be ordinary azeotropic ethanol with water; however, absolute ethanol can be used.

The tannins adsorbed by the resin are removed from it with ethanol (10 × 2 L) to give a dark brown solution. The time taken to complete one cycle on a column is <15 minutes. Ethanol is removed in a rotary evaporator under vacuum at low temperature (37 ° C), obtaining tannin (polyphenols) in the form of a dark brown powder.

In the part of the bottoms that passed through the sorbent, almost no polyphenols remain, but simple sugars, organic acids and biologically active coumarin glycosides with the smell of freshly cut hay remain. Therefore, this part of the bottom residue is evaporated under vacuum in a rotary evaporator for water to a solids content of 70% to obtain a hydrophilic food flavor.

At the same time, the sieve of the post-ejection residue, which has been well preserved in the form of a fine powder, is sieved into two fractions with a particle size of up to 150 microns (protein - carbohydrate flour) and higher (insoluble dietary fiber).

Thus, the proposed method for processing the rind of pomegranates and their seeds makes it possible to fully use the advantages of their combined two-stage extraction, first in carbon dioxide and in a mixture of carbon dioxide and ethyl alcohol under supercritical conditions, then in ethyl alcohol at atmospheric pressure. In this case, the extraction parameters are selected based on the problem to be solved to ensure maximum yield of lipophilic and hydrophilic substances without loss of valuable biologically active substances contained in them.

As you can see, the invention is a very successful alternative to analogue methods that embody an extremely irrational approach, which leads to an increase in the diversity of processing processes of the peel of pomegranate fruits and their seeds.

The invention, as well as some of the closest known methods, are based on mass transfer processes, such as extraction, distillation, adsorption, etc.

However, the invention differs significantly from analogue methods in that these processes are combined in one technology, while in analogous methods the peel and seeds are processed individually on different equipment and under different conditions, which complicates the general scheme of the technological process. In analogue methods, peel and seed extraction are carried out separately using one polar and one non-polar solvent, and the invention allows to take advantage of the stepwise extraction of lipophilic and hydrophilic fractions of the starting powder in supercritical carbon dioxide, in a mixture of supercritical carbon dioxide and ethyl alcohol and in ethyl alcohol under normal conditions. The proposed method differs from analogues in the purity of the processing process - it is carried out using harmless solvents, which cannot be said about analogous methods, and does not lead to the formation of new waste, as occurs in analogous methods. Our technology is less expensive than its counterparts, and therefore more satisfies the requirements of predictive savings. It makes it possible to avoid spending that large amount of resources in two different directions, which requires the organization of the processing of peel and seeds in a separate order. It is environmental cleanliness, a significant reduction in resource intensity and an unprecedented excess of income over expenses - that is the main thing in our technology, which small and medium-sized investors can pay attention to.

The consistency of the rationalistic approach underlying the invention begins to speak for itself already in the first stage of extraction, when it is possible to obtain not only the well-known not only SC СО ₂ extract with the properties of seed oil, but also a new lipophilic product - wax paste with the properties of fat-like substances of the pomegranate peel.

The invention is a vivid example of how, due to an extraordinary solution, it is possible, on the one hand, to reduce the amount of space and material and technical equipment needed for processing pomegranate juice production waste, and, on the other hand, to make fuller use of the available opportunities for the selective extraction and use of nutrient and biologically active substances. As a result of its implementation, one succeeds in obtaining 6 target products, combining the beneficial properties of the peel of the fruit and, at the same time, their seeds.

Selective extraction of lipophilic substances from this object in the environment of two selected solvents (1 - carbon dioxide; 2 - carbon dioxide + ethanol-water mixture containing 95% ethyl alcohol by volume) should be carried out at a pressure of at least 400 bar. Otherwise, the dissolving ability of these solvents decreases, and the process speed and yield of the target products decrease accordingly (1 - pomegranate seed oil with its peel extract; 2- and wax paste). The increase in pressure during both stages of extraction of lipophilic substances of more than 400 bar, ceteris paribus complicates the technological component of the method and increases the cost of pomegranate seed oil and wax paste.

The narrow temperature range in the 1st extraction stage is determined by the need for selective extraction of lipophilic substances from seeds and pomegranate peels. A decrease in the process temperature below 75 ° C at the indicated pressure leads to a decrease in the speed of the process and the degree of extraction of the target products. An increase in the process temperature of more than 75 ° C can lead to the decomposition of thermolabile biologically active components of natural pomegranate seed oil with an extract of its peel and wax paste and to a decrease in their biological value.

The narrow temperature range in the 2nd stage of extraction is determined by the need for quick and complete extraction of hydrophilic substances from polyfat raw materials (polyphenols, glucose, fructose, organic acids). A decrease in the process temperature below 70 ° C at atmospheric pressure leads to a decrease in the process speed. Raising the process temperature of more than 70 ° C can transfer part of the alcohol from liquid to vapor state and complicate the technological part of the process.

The temporary regime of extraction of raw materials under these conditions is determined empirically by the maximum yield of the target products.

Evaporation of all liquid solutions is carried out at relatively low temperatures under vacuum. This is determined by the need to protect from the harmful thermal effects of the substances of the thermolabile components of the raw materials and reduce the cost of the target products (which is mainly determined by the energy expended to remove alcohol and water from them).

Sieving the post-extraction residue with a well-preserved fine powder into two fractions with different particle sizes is necessary so that the bulk of the protein, starch, simple Sugars and soluble pectin (which in smaller pieces of the original powder contains much more than in larger ones) passed into a finely divided fraction with a particle size ≤150 microns (protein - carbohydrate flour), and so that in the coarsely dispersed part (> 150 microns) there remained mainly lignin, hemicellulose, protopectin and some cellulose (which are fine with come together in a complex with the name "insoluble dietary fiber").

Thanks to these distinctive features, the technology becomes extremely viable. After all, its introduction promises specialized enterprises for the production of pomegranate juice additional revenues and reduced costs of non-productive nature, since nothing more will have to be disposed of in a landfill. Now this “nothing” in terms of tonnage can be equated to half of the total amount of feedstock, i.e. Fresh pomegranate fruits.

The invention is illustrated by tables and figure.

Table 1 presents the average statistical data on the technical composition of 25 varieties and forms of pomegranate (Stronghold of the Research Institute for Fruit and Tea Growing, Geokchay, Azerbaijan). It can be seen that the complex with the general name “peel” (peel + internal partitions + placental outgrowths) accounts for an average of 40.1%, for seeds (without the surrounding juicy shell) - 14.4% of the total weight of the pomegranate fruit, the ratio between peel and seeds is 2.8: 1.

It was experimentally established that after drying, the weight of the peel and seeds decreases, compared with their initial weight, by about 3 and 2 times, respectively, and this ratio will become equal to 7 (peel) / 3 (seeds), which is followed in the invention when mixing peel and seeds for the purpose of their further joint processing.

Any other ratio is not consistent with the balance between these parts of pomegranate after drying, and may interfere with their joint processing according to the invention in places of their direct formation in pomegranate juice plants rhythmically, under conditions of full supply of both of the above components.

Drying of individual peel and individual seeds or pulp is carried out in an IR dryer at relatively high temperatures of 130-140 ° C, since this significantly shortens the drying time up to 15-30 minutes, which positively affects the color and other quality indicators of the obtained dry semi-finished products . Drying is carried out to a residual water content of ≤10%, since with a higher residual water content of 13-14%, the extraction efficiency of lipophilic substances decreases.

Solvents and parameters for both stages of extraction are selected for reasons of obtaining economic benefits from extracting the maximum amounts of lipophilic and hydrophilic substances with the lowest solvent consumption.

Experiments with the extraction of lipophilic substances from this composition in the Sosklet apparatus showed that when using polar solvents such as diethyl ether, tetrachlorethylene, hexane, etc., significant lipid oxidation occurs. In this regard, in the process of isolation, searches were undertaken for other, more efficient extraction methods.

It was found that a sufficiently complete extraction of lipophilic substances with a relatively low molecular weight (the highest quality fraction in the composition of pomegranate seed oil) without significant oxidation can be achieved by CO ₂ extraction.

As a solvent, CO ₂ gas as a fluid (supercritical state) significantly exceeds in its properties CO ₂ gas as a liquid (subcritical state), and it well extracts any free non-polar compounds with a molecular weight of up to 2000 daltons from plant materials. Strongly bound lipids are not extracted from the raw material.

Therefore, after the processing using as solvent SC CO ₂ in the raw materials still remains a certain amount of lipophilic substances with a higher molecular weight.

It was found that for the extraction of this part of the lipids from the initial mixture, a mixture of carbon dioxide and ethyl alcohol can be used. Ethyl alcohol used as a co-solvent weakens the strength of the lipid-protein complex, which ensures the completeness of extraction with a non-polar solvent, which is CO ₂ . But in our method a mixed solvent is assigned not so much this, but a different role, which will be discussed more.

Also, the efficiency of extraction largely depends on the degree of destruction of the cellular structure of the studied object. For this used grinding product.

The characteristic range of grinding raw materials with a residual moisture content of ≤10% using a disintegrator was also determined empirically and is 3-1 mm for the peel and seeds. Moreover, even with particle sizes greater than 5 mm, the speed and degree of extraction of lipophilic substances are markedly reduced.

Tab. 2 contains data on some results of CO ₂ - extraction of a mixture of the peel of pomegranate fruits (210 g) and their seeds (90 g) in the form of a powder with a particle size of 3-1 mm with a moisture content of 10 wt. %

From this table it can be seen that the highest yield of SC CO ₂ extract with the properties of pomegranate seed oil gives CO ₂ - extraction of a mixture of the peel of pomegranate fruits (210 g) and their seeds (90 g) in the form of a powder with a particle size of 3-1 mm s humidity 10 wt. % for 2 hours at a temperature of 75 ° C and a pressure of 400 bar with a solvent flow of 100 g / min.

With such a relatively tough regime, along with the free polar substances of the seeds, fat-like substances of the peel begin to be extracted. However, this does not lead to a deterioration in the quality of the CO ₂ extract with the properties of pomegranate seed oil, since wax and other fat-like substances transferred to the extract from the peel, when pressure is released, instantly harden and are not removed through the bottom tap, remaining in the fractions collector. It was found that these substances no longer harden and are easily removed with the help of a bottom tap after another stage of extraction with carbon dioxide in the presence of a modifier (ethyl alcohol). Therefore, they decided to subtract the last 30 minutes from the total time of this experiment No. 8 and transfer them to the second stage of extraction with a mixture of CO ₂ (99 wt.%) And 95% ethanol (1 wt.% Of the total weight of the mixed solvent). We also decided not to mix the extract from the second stage with the extract from the first stage and finish the second stage by obtaining our target product containing wax and other lipophilic substances of the peel.

Table 3 contains data on some results of extraction of a mixture of the peel of pomegranate fruits (210 g) and their seeds (90 g) with the appearance of a homogeneous powder with a particle size of 3-1 mm with a mixture of carbon dioxide and 95% ethyl alcohol, depending on the technological parameters used ( time, pressure, temperature).

As can be seen from it, an increase in the consumption of the modifier in such a sequence as 1; 4.2 and 6.2 wt. % of the total mass of the mixed solvent, does not lead to an increase, but, on the contrary, to a decrease in the degree of extraction of the total amount of lipophilic and hydrophilic substances, respectively, from 12.28 to 11.27 and 11.17 wt. % and the yield of lipophilic extract, respectively, from 10.95 to 8.57 and 6.10 wt. % of the total mass of the starting mixture.

The more co-solvent was taken, the greater were its losses during depressurization in the system. Therefore, for the 2nd stage, we chose the ratio between CO ₂ and ethyl alcohol, as in experiment No. 3 (Table 3): CO ₂ (99.0 wt.%, Flow rate - 99.0 g / min) / 95 % ethanol (1.0 wt.% of the total weight of the mixed solvent, flow rate 1.0 g / min).

The solid residue from the first stage of extraction is almost completely defatted, which makes it relatively easy to extract a hydrophilic complex from it.

Table 4 contains data on the content of different groups of hydrophilic substances in a mixture of peel (210 g) and seeds (90 g) of pomegranate with the appearance of a homogeneous powder with a particle size of 3-1 mm and in each separately taken part of it before extraction and after 1 2nd and 2nd stages of extraction according to the invention.

As can be seen from this table, the main result of the two-stage extraction according to the invention was the extraction of lipophilic and hydrophilic substances in an amount of about 53.3 wt. % of the total mass of the mixture with an initial water content of 9.53 g / 100 g.

This became possible mainly due to the fact that the main (by mass) component of the extraction object is the peel, which is a natural storehouse of hydrophilic substances, including polyphenols.

The remainder of the two stages of extraction contains 2.60 wt. % water-soluble polyphenols, which is much lower than their content in the original powder before its extraction (9.73 wt.%). With a residual content of water-soluble polyphenols of 2.6 wt. The% antioxidant potential of the insoluble residue should remain at a rather high level, but they will no longer be able to interfere with the digestibility of the protein.

Also, the remainder of the two stages of extraction contains 13.40 wt. % protein, which is approximately 2 times its content in the original powder before its extraction (6.27 wt.%). Protein substances of the peel include such essential amino acids as asparagine, glutamine, alanine, valine, leucine, threonine, arginine, phenylalanine, lysine, etc. [Eshmatov F.Kh. Amino acid composition of pomegranate peel / F.Kh. Eshmatov, S.Sh. Kysymova, S.K. Akhtamova // Storage and processing of agricultural raw materials, 2014. - No. 8. - from. 30-32].

Two-stage extraction also led to a significant difference between the initial powder and the post-extraction residue in the content of dietary fiber (19.47 wt.% Versus 41.30 wt.%, Respectively) and in the fat content (11.40 wt.% Against 5.0 wt.%, Respectively )

The concentration of monosaccharides in the insoluble residue decreased to 6.95 wt. % (in the initial mixture of monosaccharides was several times greater - 31.94 wt.%), sucrose - up to 0.94 wt. % (2.90%), organic acids - up to 1.23 wt. % (6.58%), vitamin C - up to 6.90 mg / 100 g (21.51 mg / 100 g).

In the proposed method, the extraction of hydrophilic substances is carried out with a water-alcohol mixture with an ethanol concentration of 95 ± 0.2% vol. at a temperature of 70 ° C in four cycles of 30 minutes each, with a ratio between the residue of raw materials from the 1st extraction stage and the solvent 1: 4.

Further (and after the fourth cycle) extraction of hydrophilic substances in order to achieve a higher degree of extraction, although possible, it is not carried out for reasons of economic efficiency, taking into account the yield of the target components and the costs of their extraction and regeneration of the solvent.

The functionality of the proposed technology and the resulting products are well captured in Fig.

It can be seen that in the processing of waste products of pomegranate juice in the form of individual peel of pomegranates and their individual seeds according to the proposed method there is no place for new waste. In essence, this is a focused process for obtaining 6 pomegranate ingredients from the same sample of raw materials one after another for the products of the cosmetic, pharmaceutical and food industries.

Example 1. Obtaining pomegranate ingredients from by-products of the production of pomegranate juice in the form of an individual dry semi-finished product of the pomegranate peel and an individual dry semi-finished product of their seeds.

Dry prefabricated peel in the amount of 12.6 kg with a residual moisture content of 10% and dry prefabricated seeds in the amount of 5.4 kg with a residual moisture content of 8% (total 18 kg) are crushed in a disintegrator to a particle size of 1-3 mm, loaded into СО ₂ - an extractor with a working volume of at least 60 l, after which the entire system is subjected to evacuation.

The extraction of the mixture of peel and seeds of pomegranate in a CO ₂ extractor is carried out first in the order of the first stage of extraction, which is carried out in two time stages with a water module (the ratio between the feed and the total amount of solvent used) in the first stage is 1:30, in the second - 1:10.

In its first stage, carbon dioxide is used as a solvent, which is fed to the extractor, separator and high-pressure cylinder at the beginning of the working process and the necessary thermodynamic parameters are set in the CO ₂ extractor, in this case a pressure of 40 MPa and a temperature of 75 ° C. The extraction process at these parameters is carried out for 1.5 hours, after which time the solvent flow is shut off, the pressure in the system is completely relieved by passing the outgoing solvent through the fraction collector (separator), and SK СО ₂ is extracted using the bottom tap; properties of pomegranate seed oil.

Then, the second stage of the 1st stage of extraction is carried out in a CO ₂ extractor, for which a mixture of carbon dioxide and ethyl alcohol is supplied to the extractor, separator and high pressure cylinder (in this case, ethyl alcohol is used in an amount of 1 wt.%, And carbon dioxide is used 99 wt.% Of the total solvent mass) and set the necessary thermodynamic parameters (pressure 40 MPa and temperature 75 ° С) in a СО ₂ - extractor. The extraction process at these parameters is carried out for 0.5 hours, after which time the solvent flow is shut off, the pressure in the system is completely relieved, passing the outgoing solvent through the fraction collector (separator), and the wax paste is removed using a bottom valve.

To both target products from the 1st stage of extraction, before packaging, add 0.005 wt. % rosemary antioxidant extract.

The 2nd extraction stage is carried out in a glass reactor (where the solid residue from the 1st extraction stage is transferred) with a water-alcohol mixture with an ethanol concentration of 95 ± 0.2% vol. at a temperature of 70 ° C in 4 cycles of 30 minutes each with a ratio between the extracted material and the solvent (hydraulic module) at the beginning of each of these cycles 1: 4.

Each such cycle begins with feeding into the reactor (with a working volume of 100 l) a solvent in an amount of ≈64 l (taking into account that the weight of the feedstock decreased slightly after the 1st extraction step, and the hydraulic module should be equal to 1: 4) and end with separation under the pressure of the resulting extract through the bottom drain valve.

The extracts as they are separated are sent to the apparatus for the regeneration of the solvent from natural extracts - alcohol separator (per 100 l).

In the apparatus, all alcohol is distilled off under vacuum (the end of the process is judged by the specific smell characteristic of alcohol).

As a result of such processing of extracts from all 6 cycles, a dark brown aqueous bottoms residue is formed in a volume of about 16 L with a content of 43 ± 2% dry solids, which are divided into 2 L parts and introduced into the vacuum aspiration column of the solid-phase extraction (TFE) system. where they pass through Amberlite XAD-16 adsorption resin (5 kg), which holds polyphenols on its surface.

After the target substance is retained by the sorbent, the sorbent is washed from foreign impurities. Why distilled water is passed through it until the sweet pale yellow eluate becomes clear (usually 40 l of water). The remaining water is removed from the resin by vacuum aspiration.

At the final stage, quantitative elution of the target component occurs.

The tannins adsorbed by the resin are removed from it with ethanol (10 × 2 L) to give a dark brown solution. The time taken to complete one cycle on a column is <15 minutes. Ethanol is removed in a rotary evaporator under vacuum at low temperature (37 ° C), obtaining tannin (polyphenols) in the form of a dark brown powder.

In the part of the bottoms that passed through the sorbent, almost no polyphenols remain, but simple sugars, organic acids and biologically active coumarin glycosides with the smell of freshly cut hay remain. Therefore, this part of the bottom residue is evaporated under vacuum in a rotary evaporator for water to a solids content of 70% to obtain a hydrophilic food flavor.

At the same time, the sieve of the post-ejection residue, which has been well preserved in the form of a fine powder, is sieved into two fractions with a particle size of up to 150 microns (protein-carbohydrate flour) and higher (insoluble dietary fiber).

While SK СО ₂ is an extract with the properties of pomegranate seed oil, wax paste and food flavoring are stored under conditions of absolute sterility and the container must have screw caps for packing loose products (tannin, protein-carbohydrate flour, insoluble food fibers) wide-necked cans of transparent plastic with a lid are quite suitable as a practical and convenient container.

As a result of extraction of the lipophilic and hydrophilic fractions and further processing of the post-extraction residue, when the content of 18 kg of polyphenols in the feedstock was 2.306 kg, simple sugars 5.500 kg, protein 1.120 kg, organic acids 1.202 kg, fat 2.210 kg and fibers 3.700 kg, a total of 12.250 kg was obtained (100%) of products, including 0.620 kg (5.06%) of SC СО ₂ - extract with the properties of pomegranate seed oil, 0.206 kg (1.68%) of wax paste, 1.998 kg (16.31%) of tannin, 5.100 kg (41.63%) of food flavoring, 2.105 kg (17.18%) of protein-carbohydrate flour and 2.221 kg (18.14%) of insoluble dietary fiber.

Example 2. Obtaining pomegranate ingredients from a by-product of the production of pomegranate juice in the form of a dry semi-finished pulp of fruit.

Dry prefabricated pulp of fruits in the amount of 18 kg with a residual moisture content of 9% is crushed in a disintegrator to a particle size of 1-3 mm, loaded into a CO ₂ extractor with a working volume of at least 60 l, after which the entire system is subjected to vacuum.

The extraction of the mixture of peel and seeds of pomegranate in a CO ₂ extractor is carried out in the order of implementation of the 1st stage of extraction, which is carried out in two time stages with a water module (the ratio between raw materials and the total amount of solvent used) in the first stage is 1:30, in the second -1 :10.

In its first stage, carbon dioxide is used as a solvent, which is fed to the extractor, separator and high-pressure cylinder at the beginning of the working process and the necessary thermodynamic parameters are set in the CO ₂ extractor, in this case a pressure of 40 MPa and a temperature of 75 ° C. The extraction process at these parameters is carried out for 1.5 hours, after which time the solvent flow is shut off, the pressure in the system is completely relieved by passing the outgoing solvent through the fraction collector (separator), and SK СО ₂ is extracted using the bottom tap; properties of pomegranate seed oil.

Then, the second stage of the 1st stage of extraction is carried out in a CO ₂ extractor, for which a mixture of carbon dioxide and ethyl alcohol is supplied to the extractor, separator and high pressure cylinder (in this case, ethyl alcohol is used in an amount of 1 wt.%, And carbon dioxide is used 99 wt.% Of the total solvent mass) and set the necessary thermodynamic parameters (pressure 40 MPa and temperature 75 ° С) in a СО ₂ - extractor. The extraction process at these parameters is carried out for 0.5 hours, after which time the solvent flow is shut off, the pressure in the system is completely relieved, passing the outgoing solvent through the fraction collector (separator), and the wax paste is removed using a bottom valve.

To both target products from the 1st stage of extraction, before packaging, add 0.005 wt. % rosemary antioxidant extract.

The 2nd extraction stage is carried out in a glass reactor (where the solid residue from the 1st extraction stage is transferred) with a water-alcohol mixture with an ethanol concentration of 95 ± 0.2% vol. at a temperature of 70 ° C in 4 cycles of 30 minutes at a ratio between the extracted material and the solvent (hydraulic module) at the beginning of each of these cycles 1: 4.

Each such cycle begins with feeding into the reactor (with a working volume of 100 l) a solvent in an amount of ≈64 l (taking into account that the weight of the feedstock decreased slightly after the 1st extraction step, and the hydraulic module should be equal to 1: 4) and end with separation under the pressure of the resulting extract through the drain valve located at the bottom of the reactor.

The extracts as they are separated are sent to the apparatus for the regeneration of the solvent from natural extracts - alcohol separator (per 100 l).

In the apparatus, all alcohol is distilled off under vacuum (the end of the process is judged by the specific smell characteristic of alcohol).

As a result of such processing of extracts from all 6 cycles, a dark brown aqueous bottoms residue is formed in a volume of about 16 L with a content of 43 ± 2% dry solids, which are divided into 2 L parts and introduced into the vacuum aspiration column of the solid-phase extraction (TFE) system. where they pass through Amberlite XAD-16 adsorption resin (5 kg), which holds polyphenols on its surface.

After the target substance is retained by the sorbent, the sorbent is washed from foreign impurities. Why distilled water is passed through it until the sweet pale yellow eluate becomes clear (usually 40 l of water). The remaining water is removed from the resin by vacuum aspiration.

At the final stage, quantitative elution of the target component occurs.

The tannins adsorbed by the resin are removed from it with ethanol (10 × 2 L) to give a dark brown solution. The time taken to complete one cycle on a column is <15 minutes. Ethanol is removed in a rotary evaporator under vacuum at low temperature (37 ° C), obtaining tannin (polyphenols) in the form of a dark brown powder.

In the part of the bottoms that passed through the sorbent, almost no polyphenols remain, but simple sugars, organic acids and biologically active coumarin glycosides with the smell of freshly cut hay remain. Therefore, this part of the bottom residue is evaporated under vacuum in a rotary evaporator for water to a solids content of 70% to obtain a hydrophilic food flavor.

At the same time, the sieve of the post-ejection residue, which has been well preserved in the form of a fine powder, is sieved into two fractions with a particle size of up to 150 microns (protein-carbohydrate flour) and higher (insoluble dietary fiber).

As a result of extraction of the lipophilic and hydrophilic fractions and further processing of the post-extraction residue, with a content of 18.10 kg of polyphenols 2.106 kg, simple sugars 5.300 kg, protein 1.080 kg, organic acids 1.000 kg, fat 2.016 kg and fibers 3.400 kg, only 12 kg products, including 0.600 kg of SC CO ₂ -extract with the properties of pomegranate seed oil, 0.196 kg of wax paste, 1.688 kg of tannin, 4.500 kg of food flavoring, 2.405 kg of protein-carbohydrate flour and 2.621 kg of insoluble dietary fiber.

Claims (1)

A method of processing by-products of the production of pomegranate juice to obtain a lipophilic complex, polyphenols and food additives, including drying by-products, grinding and extraction of lipophilic and hydrophilic fractions, characterized in that the by-products are dried to a residual water content of <10 wt.%, The products are ground drying them to particles with a size of 1-3 mm, after which the products from drying and grinding of the individual peel and individual seeds are combined together in a weight ratio of 7: 3 or use ucts drying and crushing the fruit pulp, which is already ready for further processing by the extraction mixture with same balance between the peel and seeds, the extraction is carried out in two steps: a first step of extraction is conducted in a CO ₂ -ekstraktore at a temperature of 75 ° C and a pressure 400 bar, first for 1.5 hours with carbon dioxide at 1:30 hydromodule to obtain a supercritical CO ₂ extract with the properties of pomegranate seed oil in the first stage, then another 0.5 hours with a mixture containing 99 wt.% Carbon dioxide and 1 wt. .% ethyl alcohol with conc by centration of 95 ± 0.2 vol.%, with a hydraulic module of 1:10 to obtain a wax paste with the properties of fat-like substances of its peel in the second stage, the second extraction stage is carried out in a glass reactor with an aqueous-alcohol mixture with an ethanol concentration of 95 ± 0.2 vol % at a temperature of 70 ° C in 4 cycles of 30 minutes each with a ratio between the residue of the raw material from the first extraction stage and a solvent of 1: 4, with the separation of four portions of polyphenol-containing extracts, one portion in each cycle, and sending them the least separation in the alcohol separator, where of them distillation alcohol is removed under vacuum to a predetermined dry matter content in the bottom residue, after which the aqueous portion of the extract remaining after alcohol removal is discharged from the working capacity of the alcohol separator and introduced in parts into the vacuum aspiration column of the solid-phase extraction system, where it passes through the Amberlite XAD-16 adsorption resin , after the target substance is retained by the sorbent, as judged by the color of the extract: first it is dark brown, after holding the polyphenols with the resin it turns pale yellow, the sorbent is washed nt from foreign impurities, for which distilled water is passed through it until the sweet pale yellow eluate becomes transparent, the remaining water is removed from the surface of the resin by vacuum aspiration, the polyphenols bound to it are washed off with ethanol to obtain a dark brown solution, ethanol removed in a rotary evaporator under vacuum at a low temperature of 37 ° C, obtaining polyphenols in the form of a dark brown powder, and that part of the aqueous extract that passed through the sorbent is evaporated under vacuum to a dry matter content of 70 m wt.% to obtain a hydrophilic food flavoring, at the same time, the post-ejection residue, which retains the shape of a fine powder, is sieved into two fractions with a particle size of up to 150 microns protein - carbohydrate flour and above - insoluble dietary fiber.

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