RU2610312C1 - Method to produce pectin from plant raw materials - Google Patents

Abstract

FIELD: food industry.

SUBSTANCE: invention relates to food, pharmaceutical and biochemical industries. Method of pectin production includes extraction of pectin-containing pomaces by solution of food or mineral acid with pH of 0.8-3.2 and hydraulic module of 1:(15-45) for 1-6 hours at temperature of 70-95°C, filtration of produced extract, its treatment. Then extract is concentrated on a cascade of ion-exchange and adsorption columns, ultrafiltration and diafiltration plants with polymer membranes with cut off at 20-100 kDa. Produced pectin solution is dried at temperature of 45-95°C to produce pectin in drying belt vacuum deviced with subsequent grinding of pectin or devices of spray type. Besides, removal of ballast substances in ion exchange and adsorption processes is carried out on cation exchange resins AMBERLITE® FPC23 H, anion exchange resins AMBERLITE® FPA90 Cl and adsorption resins AMBERLITE® FPX66.

EFFECT: invention makes it possible to increase yield of pectin, extent of purity and to produce pectin with specified molecular mass.

7 cl

Description

The invention relates to food, pharmaceutical and biochemical industries and can be used in the production of pectin from plant materials with the necessary characteristics, with the exception of the traditional stages of alcohol deposition and concentration on vacuum-evaporation plants.

It is known that due to the complex structure of its molecule, the basis of which is polygalacturonic acid, pectin has the properties of biologically active substances, which allows it to be actively used for therapeutic and prophylactic purposes.

Pectins or pectin substances are polysaccharides formed mainly by galacturonic acid residues. An analysis of domestic and foreign developments shows that the composition and structure of pectin substances cannot be considered finally studied at this stage of the development of science (Smidaroed O. Structure and properties of charged polysaccharides // Intern. Congr. Pure Appl. Chem. / Proc. - 1980. - 27th. - P. 315-327.)

In 1951, the classification of pectin substances was clarified by the scientist Kertes (Kertes) and currently has the following form (GOST R51806-2001):

Pectin: A dry, powdery product from light beige to light gray in color, consisting primarily of polygalacturonic acid, partially sodium esterified with methanol, and its sodium, potassium, calcium and ammonium salts, in which the mass fraction of galacturonic acid in the dry dehydrated material is not less than 65% , isolated from the plant tissue of higher plants, with stabilizing, thickening, gel-forming ability and functional properties, intended for use simultaneously with food and and for use as a food additive, or physiologically functional food ingredient.

Polygalacturonic acid: An acid that is a linear polymer whose molecule consists of 1,4-glycosidic linkages of α-D-galacturonic acid residues and a certain amount of L-ramnose residues.

Highly esterified pectin: Pectin in which the degree of esterification of carboxyl groups in a polygalacturonic acid molecule is equal to or more than 50%.

Low esterified pectin: Pectin in which the degree of esterification of carboxyl groups in a polygalacturonic acid molecule is less than 50%.

Amidated pectin: A low esterified pectin in which part of the ether groups in the polygalacturonic acid molecule is replaced by amide groups, with the degree of amidation not exceeding 25% and the mass fraction of nitrogen after treatment with acid and ethanol not exceeding 2.5%.

Pectic acid: Polygalacturonic acid, in the molecule of which part of the carboxyl groups is esterified with methanol.

Pectinate: Pectic acid salt.

Pectic acid: Polygalacturonic acid isolated from pectic acid by hydrolysis of ester groups.

Pectate: Pectic acid salt.

Pectin substance: A substance consisting of pectic acid, pectinates, neutral polysaccharides. Neutral polysaccharides include arabinan and galactan.

Protopectin: A water-insoluble natural form of pectin contained in the plant tissue of higher plants, hydrolyzable in the presence of chemicals or enzymes to form pectin when extracting plant materials in an aqueous medium.

Pectin-containing product: A dry, powdery or liquid product consisting of polygalacturonic acid partially esterified with methanol and its sodium, potassium, calcium and ammonium salts, components of plant tissues of higher plants, in which the mass fraction of galacturonic acid in a dry desalted substance is from 50% to 65% .

Pectin product: A dry, powdery or liquid product consisting of polygalacturonic acid partially esterified with methanol and its sodium, potassium, calcium and ammonium salts, components of plant tissues of higher plants, in which the mass fraction of galacturonic acid in a dry anhydrous substance is less than 50%.

As a result of numerous studies, scientists came to the conclusion that pectin can be considered as a mixture of three polysaccharides: pectic acid, galactan, arabinan. Pectic acid, in addition to D-galacturonic acid, includes neutral sugars: L-arabinose, D-galactose, L-rhamnose.

Pectin is assigned the code of food additive E-440.

One of the most important properties of pectins is their gelling ability. Gelling is a process in which a hot pectin-containing solution, when cooled, forms a dense body of a given shape, while binding a large amount of liquid.

A feature of pectin as a builder is the ability to form gels in aqueous solutions only in the presence of a certain amount of sugar and acid and / or calcium ions.

Pectin has an active complexing ability.

Authors of the article Verfahren zur Herstellung von Fleischerzeugnissen / Westphal Gunter, Sielaff Heinz, Oelker Peter, Ehwald Rudolf; Humboldt Universitat zu Berlin. Pat. 258743 MKI4 A23L 1/317. - 1988 show that all structural units of pectin substances possess pharmacological activity.

The use of pectin for preventive and therapeutic purposes is associated with:

1. With the complexing ability of the pectin molecule and its ability to bind heavy and radioactive metal ions. Detailed studies are described in the articles:

Khotimchenko M.Yu., Kovalev V.V., Ziganshina O.A. Assessment of enterosorption activity of various sorbents in case of lead damage in experimental animals // Biologically active food additives: XXI century: Mat. IV Int. Symposium. - M .; VIP Publishing, 2000 .-- S. 271-272.

Khotimchenko M.Yu., Khasina E.I., Kovalev V.V. The effectiveness of food non-starch polysaccharides in experimental toxic hepatitis // Nutrition Issues, 2000, v. 69, No. 1-2. - S. 22-26.

2. With an effect on intercellular interactions leading to normalization of immunity. Positive results of the use of pectin in the treatment of cancer are given in the works of scientists from different countries:

Sergeev A.V. The use of pectins as non-toxic immunomodulators in oncology // Chemistry and Usp. extractive. substances of the tree: Tez. doc. 3 All n.-t. conf. - Gorky, 1990 .-- S. 113-114.

Pienta K.J. Inhibition of spontaneous metastasis in a rat prostate cancer model by oral administration of modified citrus pectin // 1. Natl. Canser Inst, 1995, 1-87 (5). - P. 348-353.

Platt D. Modulation of the lung colonization of B16: fl melanoma cell by (modified) citrus pectin // 1. Natl. Cancer Inst, 1992, 84 (6). - P. 438-442.

Raloff J. Pectin helps fight cancer’s spread // Science news, 1992, vol. 141, No. 12. - P. 180.

3. With sorption ability, which allows the active use of pectin in the prevention of chronic non-communicable diseases, therapeutic and surgical practice, in the normalization of metabolic processes in the body, in particular, lowering LDL cholesterol in human blood plasma, glycemic and insulinemic reactions.

Olsen Roger A. Hydrocolloid - adhesive composition. Patent 4952618, adhesive composition. Patent 4952618, USA, MKI5 A61L 15/00, C08L 1/00. - 1990.

Mosbcy Deral T. Wound filling compositions. Patent 4956350, USA, MKI5 A61K 31/00, C08B 37/00. - 1990.

Matheson H.V., Coon I.S., Story J.A. Cholesterol 7-alpha-hydroxylase activity is increased by dietary modification with psyllium hydrocolloid, pectin, cholesterol and cholestyramine in rats // J. Nutr., 1995, vol. 125, No. 3. - P. 454-458.

Tiwary S.M., Ward J.A., Jakson B.A. Effect of pectin on satiety in healthy US Army adults // J. Amer. Coll. Nutr., 1997, vol. 16, No. 5. - P. 423-428.

Veldman F.J., Nair C.H., Vorster H.H. Possible mechanism through which dietary pectin influences fibrin network architecture in hypocholesterolemic subjects // Thromb. Res., 1999, vol. 93, No. 6. - P. 253-264.

Bykov A.T. Restorative medicine and human ecology M., GEOTAR-Media, 2009-699 p.

Tutelian V.A., Baygarin E.K., Pogozheva A.V. Dietary fiber: hygienic characterization and evaluation of effectiveness. M .: SvR-Argus, 2012 - 244 p.

4. With the ability to form gels on the surface of the mucous membrane of the stomach and intestines, change the viscosity of the contents of the stomach and intestines, and when exposed to intestinal enzymes, form the acids necessary for the body:

Clausen M.R., Moriensen R.V. Kinetic-studies on the metabolism of short-chain fatty-acids and glucose by isolated rat colonocytes // Gastroenterology, 1994, vol. 106, No. 2. - P. 423-432.

Scheppach W. Effects of short-chain fatty-acids on gut morphology and function // Gut., 1994, vol. 35, No. 1. - P. 35-38.

Tiwary S.M., Ward J.A., Jakson B.A. Effect of pectin on satiety in healthy US Army adults // J. Amer. Coll. Nutr., 1997, vol. 16, No. 5. - P. 423-428.

Lim B.O., Yamada K., Proll J. Dietary fibers modulate indices of intestinal immune function in rats // J. Nutr., 1998, vol. 127, No. 5. - P. 663-667.

Nie Y., Li Y., Wu Y. Colloidal vismuth pectin: an alternative to vismuth subcitrate for the treatment of Helicobacter pylori-positive duodenal ulcer // Helicobacter., 1999, vol. 4, No. 2. - P. 128-134.

Pectins are an aid in the preparation of many dosage forms, serve as the basis for the preparation of lozenges, suppositories, and are the raw material in the preparation of hydrogels, tablets, soft gelatine and rectal capsules, and candles. Their prolonged action is used in tablets, potions with different drugs.

Known methods for producing pectin, suggest:

- the use of cavitation treatment for hydrolysis-extraction of pectin-containing raw materials in a hydroacoustic extractor-disintegrator, the concentration of the filtrate on ultrafiltration membranes on a solid substrate with a pore diameter of (1-10) ⋅ 10 ^-9 m, thickening in a vertical two-case direct-flow circulation-film vacuum-evaporation apparatus and drying at a temperature of 75-92 ° C (patent RU 2066962 C1, publ. 09/27/1996). The main disadvantages of the method are the difficulties of maintaining a standard cavitation mode, high energy consumption of the process.

- the use of electroactivated water for the hydrolysis-extraction of pectin substances, drying the pectin extract by spraying at a temperature of a drying agent of 80-180 ° C and processing the dried extract with a mixture of ethanol and electroactivated water, followed by further treatment with ethanol (patent RU 2080081 C1, publ. 27.05.1997 ) The main disadvantages of the method are the high energy consumption of the process required to obtain electroactivated water, the instability of the pH of this medium, the high temperature of the drying agent, the use of alcohol, which leads to a rise in the cost of the process and loss of processability.

- carrying out hydrolysis with Baliz-2 or Baliz-B at an acidity of 0.2-1.2 with the preliminary swelling of pectin-containing raw materials, washing with distilled water at least 4 times, followed by extraction. Hydro module 1: 10-12 during the first extraction and 1: 10-14 during the second extraction of pomace. Filtration of the hydrolyzate, its passage through ion-exchange resins, concentration, precipitation of pectin, washing with alcohol, drying (patent RU 2114122 C1, publ. 27.06.1998). The disadvantage of this method is the use of alcohol for purification and isolation of pectin, which leads to a rise in the cost of the process, an increase in labor and energy costs.

Known methods for the isolation of pectin from plant materials using a solution of citric acid (patent RU 2144827 C1, publ. 01/27/2000, patent RU 2110187 C1, publ. 10.05.1998). The extraction of pectin and its purification are carried out using ethanol, which, in the conditions of industrial production, leads to a rise in the cost of the process and, accordingly, of the final product.

Thus, the above methods are energy and labor-intensive processes, which ultimately leads to an increase in the cost of the final product.

In the patent RU 2322456 C1 (publ. 20.04.2008) a method for producing pectin is disclosed, which consists in treating pre-ground vegetable raw materials with a solution of chloroform and ethanol prepared in a ratio of 1: 3, taken respectively in a ratio of 1: 6, followed by extraction on a water bath at a temperature of 75-80 ° C for 30-40 minutes, followed by filtering the plant material to separate the first extract; filtered vegetable raw materials are poured with distilled water at a temperature of 60-70 ° C, respectively, in a ratio of 1:18 and extracted in a water bath at a temperature of 90-95 ° C for one hour, followed by filtering of the vegetable raw material to separate the second extract; the filtered plant material is poured with a 0.3-0.5% solution of oxalic acid ammonium, respectively, in a ratio of 1:15 and extracted in a water bath at a temperature of 75-80 ° C for 30-40 minutes, followed by filtering of the plant material for separation third extract; filtered vegetable raw materials are poured with a 0.4-0.5% hydrochloric acid solution and heated at a temperature of 75-80 ° C for one hour, followed by filtering the vegetable raw materials to separate the fourth extract, which is mixed with the first, second and third extracts ; the resulting solution is neutralized with ammonium hydroxide to pH 7, precipitated with 96% ethanol, respectively, in a ratio of 1: 3 at room temperature; the resulting precipitate is squeezed and dried at a temperature of 4-6 ° C.

Patent RU 2124848 C1 (publ. 20.01.1999) discloses a method for producing pectin, which includes washing the raw materials, hydrolysis-extraction, separation of the hydrolysis mixture to isolate the pectin extract, treating the pectin extract with an anion exchange resin, treating pectin with ethyl alcohol, characterized in that after isolation the pectin extract is further purified; before processing with an anion exchange resin, the pectin extract is treated with a cation exchange resin at a ratio of the specific consumption of anion exchange resin to cateonite of 1.3-1.4 s ³ / cm ³ of the extract and processing is carried out dry pectin with ethanol. The H ⁺ cationic pectin extract is treated with an EDE-10P anion exchange resin in an OH ^- form.

International application WO 2012167963 A1 (published December 13, 2012) discloses a method for the extraction of pectin having a high degree of polymerization using ion exchange resins Lewatit® SI 668, Lewatit® SI 468, Purolite® CUOE and Amberlite® SRIL Na.

International application WO 2015091629 A1 (publ. 06/25/2015) discloses a method for the extraction of calcium-sensitive pectin, in which the purified juice is subjected to ion exchange on a weakly acidic resin Amberlite C200 mainly in sodium form.

The problems of the prior art are partially overcome in the claimed invention.

The technical result of the proposed method is an improved extraction of pectin substances from plant materials, purification, concentration of pectin solutions and obtaining dry pectin with the desired qualitative and quantitative indicators.

Examples of qualitative and quantitative indicators of pectin obtained by the present method from certain types of pectin-containing raw materials are shown in Table No. 1.

The achievement of the technical result is influenced by the choice of specific stages and conditions for their implementation. The study of the complex process parameters expectedly led to the achievement of a technical result not following from the prior art. The parameters are shown in Table No. 2 for an example of apple squeeze processing (Russia).

The proposed method for producing pectin includes the extraction of pectin-containing pomace with a solution of food or mineral acid with a pH of 0.8-3.2 and a water module of 1: (15-45) for 1-6 hours at a temperature of 70-95 ° C, filtering the obtained extract, its purification and concentration on a cascade of ion-exchange and adsorption columns, ultrafiltration and diafiltration units with polymer membranes with a cut-off of 20-100 kDa and subsequent drying of the obtained pectin solution at a temperature of 45-95 ° C to obtain pectin in a drying belt vacuum apparatus with subsequent grinding of pectin or spray-type apparatuses, where the ballast substances are removed during ion-exchange and adsorption processes using AMBERLITE® FPC23 Н cation-exchange resins, AMBERLITE® FPA90 Cl anion-exchange resins and AMBERLITE® FPX66 adsorption resins.

Preferably, the extraction of pectin-containing pomace is carried out with a solution of food or mineral acid with a pH of 1.3-2.1 and a water module of 1: (15-40).

Preferably, 50 kDa cutoff polymer membranes are used.

Preferably, the resulting pectin solution is dried at a temperature of 45-65 ° C.

Preferably, the removal of pectin contaminants is carried out in a cascade of ultrafiltration and diafiltration units with a ratio of solution / additional demineralized water 1: (1.5-2).

Preferably, the concentration of the pectin-containing solution is carried out on ultrafiltration membranes with a cut-off of 50 kDa to 5 ° Bx.

Preferably, the resulting concentrated pectin solution before drying has a pH of 2.5-3.5.

AMBERLITE® FPC23 H cation exchange resins, AMBERLITE® FPA90 Cl anion exchange resins, and AMBERLITE® FPX66 adsorption resins are well known in the art. The name AMBERLITE is well-established and characterizes a line of products, each of which has certain inherent properties.

Similar resins are those produced by Rohm and Haas Company and Dow Chemical Company: AMBERJET® 1500H, AMBERJET® 4400C1, AMBERLITE® FPA98 Cl, DOWEX® MONOSPHERE ™ 66, DOWEX® MONOSPHERE ™ 88, DOWEX® OPTIPORE ™ SD-2, and Food Grade Strong Acide Cation Exchange Resin (TC007) resin manufactured by Taiyuan Lanlang Technology Industrial Corp. Shanxi, China.

The pectin-containing solution is passed sequentially through two ion-exchange and one adsorption columns to purify it from unwanted ions and pigments. First, the solution enters the columns filled with AMBERLITE® FPC23 H brand resin, intended for the purification of solutions containing various sugars from calcium ions that impair the gelling properties of pectin, as well as other cations present in the solution. When the solution enters the columns filled with AMBERLITE® FPA90 Cl resin, the anions extracting food acid pectin, as well as other anions present in the solution, with the exception of pectin anions, are removed. In conclusion, the solution enters a column filled with AMBERLITE® FPX66 resin to remove pigments present in the solution and impairing the color of the pectin. The working temperature of the solutions is 50-80 ° C.

Example

Squeezes with a moisture content of 5-12% are pre-crushed, if necessary, and fed to a container for pre-soaking / swelling, where they are mixed with hot demineralized water with a temperature of 75-95 ° C in a ratio of 1:12 and aged for 0.3-1 hours with constant stirring.

The mixture of pomace and water is fed into an extractor-hydrolyzer, where it is brought by adding hot (75-95 ° C) demineralized water to hydraulic module 1: (15-45) and dosing food or mineral acid to a pH of 0.8-3.2, and aged for 1-6 hours at a temperature of 75-95 ° C and periodic stirring. The content of soluble solids in the solution reaches 1.4-1.8%, including pectin 0.5-0.7%.

The specific hydrolysis parameters are set depending on the requirements for the quantity and quality of the final product and the characteristics of the raw materials.

The mixture is cooled to a temperature of 20-50 ° C and, by two-stage extraction or decantation, with the addition of demineralized water in the second stage in the ratio: the pulp after the first stage of extraction / additional demineralized water 1: 1 is separated from the insoluble part.

An acidic pectin-containing solution at a temperature of 20-50 ° C is subjected to coarse filtration to remove the remaining large particles and microfiltration, after which it is concentrated 2 times in an ultrafiltration unit and then pre-purified in a diafiltration unit with a 1: 2 solution / additional demineralized water ratio.

The pre-concentrated and pre-purified solution is fed to cation exchange columns filled with AMBERLITE® FPC23 H resin, then to anion exchange columns filled with AMBERLITE® FPA90 Cl resin, and then to adsorption columns filled with AMBERLITE® FPX66 resin to remove contaminants and achieve the desired colors of the final product (all resins manufactured by Rohm and Haas Company or Dow Chemical Company).

The next concentration is 1.5 times and the final purification of the pectin-containing solution is carried out on the cascade of ultra-diafiltration units with a ratio of solution / additional demineralized water during diafiltration of 1: 1.5. Concentration of the solution to the content of pectin substances in it no more than 5 ° Bx is carried out on an ultrafiltration unit. All ultrafiltration and diafiltration units of the present method use polymer membranes with cut-off cutoffs of 20-100 kDa. As a result, the resulting solution has a controlled acidity of the medium with pH 2.5-3.5. The drying of pectin-containing solutions is carried out at a temperature of 45-95 ° C in a drying belt vacuum apparatus, followed by grinding of pectin or spray apparatus.

Thus, as a result of using this technology, the total yield of pectin is, in terms of dry pulp, 10-30% (depending on the raw material). After purification, native pectin with a given molecular weight is obtained, and freed from low and high molecular weight impurities, which leads to a high degree of purity of the product.

Claims (7)

1. The method of producing pectin, including the extraction of pectin-containing pomace with a solution of food or mineral acid with a pH of 0.8-3.2 and a hydraulic module 1: (15-45) for 1-6 hours at a temperature of 70-95 ° C, filtering the obtained extract , its purification and concentration on a cascade of ion-exchange and adsorption columns, ultrafiltration and diafiltration units with polymer membranes with a cut-off of 20-100 kDa and subsequent drying of the obtained pectin solution at a temperature of 45-95 ° C to obtain pectin in a drying belt vacuum apparatus with the last driving pectin grinding or spray-type apparatuses, where the ballast substances are removed during ion-exchange and adsorption processes on AMBERLITE® FPC23 Н cation-exchange resins, AMBERLITE® FPA90 Cl anion-exchange resins and AMBERLITE® FPX66 adsorption resins. 2. The method according to p. 1, characterized in that the extraction of pectin-containing pomace is carried out with a solution of food or mineral acid with a pH of 1.3-2.1 and a hydraulic module 1: (15-40). 3. The method according to p. 1, characterized in that the use of polymer membranes with a cutoff of 50 kDa. 4. The method according to p. 1, characterized in that the drying of the obtained pectin solution is carried out at a temperature of 45-65 ° C. 5. The method according to p. 1, characterized in that the removal of contaminating pectin substances is carried out in a cascade of ultrafiltration and diafiltration plants with a ratio of solution / additional demineralized water 1: (1.5-2). 6. The method according to p. 1, characterized in that the concentration of the pectin-containing solution is carried out on ultrafiltration membranes with a cut-off of 50 kDa to 5 ° Bx. 7. The method according to p. 1, characterized in that the obtained concentrated pectin solution before drying has a pH of 2.5-3.5.