JPS60108402A - Efficient manufacture of pectin from vegetable material - Google Patents

Abstract

PURPOSE:To economically and efficiently obtain high-quality pectin in high yield useful as food additive, etc., by heating following incorporation of pectin-contg. vegetable material with both acid and specific amount of chelating compound. CONSTITUTION:A pectin-contg. vegetable material (e.g. strained lees)is incorporated with (A) an aicd (e.g. hydrochloric acid, acetic acid, citric acid) (B) ca. 0.01-30wt% based on said material, of chelating compound (e.g. polyphosphate, EDTA, tartaric acid) followed by heating pref. to 40-90 deg.C to extract pection. The amount of said acid to be incorporated is pref. such that the pH of the resulting aqueous solution falls between 2 and 4. Furthermore, incorporation of ca. 0.001-10wt% based on said material, of surfactant (except cationic one) would enhance the extraction process.

Description

Detailed Description of the Invention This invention relates to an efficient method for producing vectin, and more specifically, when extracting vectin from plant raw materials, by adding a compound that has a chelating effect in addition to an acid, it is possible to add a compound that has a chelating effect to the plant as a base material for the vectin. A method that facilitates the decomposition of protopectin existing in the water into vector to obtain a high-yield vectin with excellent performance, and depending on the progress after the raw material is collected, a surfactant (however, a method consisting only of cationic surfactants) The addition of these substances promotes the swelling of not only plant tissue but also cells based on its surfactant, the decomposition of protopectin to pectin by penetration of the decomposition extract consisting of acid and chelating compounds, and the elution of pectin. The present invention relates to a production method for obtaining a vectin with good performance and quality at a good yield.

Pectin is contained in fruits, vegetables, etc., and coexists with cellulose, sugar, etc. in the cell membrane and the medial membrane that connects cells, and holds cells together. For example, it plays an important role in controlling the firmness of fruits. In unripe fruits, it exists in the form of a macromolecular water-insoluble protopectin, and as it ripens, it is decomposed into water-soluble pectin by the action of enzymes contained in the fruit. In other words, pectin is an important substance that helps in bonding between cells and the cells themselves in the plant body, thereby preserving plant tissues, and is used not only in fruits but also in leaves, stems, roots, rhizomes,
It is widely distributed in each part of the tuber plant.

Pectin is added to foods and is used as a gelling agent in the production of jelly, marmalade, etc.

Shape retention stabilizer for ice cream, sherbet, milk products, etc., quality stabilizer for soft drinks, water retention for bread,
In addition to being used as an anti-aging agent and an edible transparent coating agent for foods, it has recently attracted medical attention as a food that lowers serum cholesterol levels and reduces salt content, and as a low-calorie food.

As a conventional method for producing pectin, the following method is generally adopted in Europe and the United States. In other words, (if) The lees of fruit juice are crushed, heated to destroy enzymes and prevent the decomposition of pectin to low molecular weight, then washed with water, added acid in an aqueous system, and heated to destroy the tissue. The pectin is decomposed, the pectin is made water-soluble, the pectin extract is filtered, and the insoluble decomposition residue is purified and concentrated. (O) Then, alcohol is added to this purified concentrate to precipitate pectin. Let it settle (c)
The commonly used method is to collect this precipitate, wash it first with hydrous alcohol and then with high-purity alcohol, dry it, and grind it to produce pectin as a product. The inventor considered improvements to this production method, and as a result of carefully examining each of the steps described above, noticed that there was room for improvement in the method for extracting pectin from vegetable raw materials in step (a).

The location and form of pectin present in plants, and since pectin itself is a high molecular weight substance with a molecular weight of approximately 10,000 to 400,000, it is difficult to extract it from plant raw materials.
We speculated that conventional extraction methods would be insufficient, and as a result of our investigation, we found that, as previously described in Japanese Patent Application No. 58-000142, we made it easier for the decomposition extract to penetrate into plant tissues and cells.
In addition, a small amount of cationic surfactant is added to the decomposition and extraction aqueous solution in order to extract as much pectin contained in the plant body as possible by utilizing the surfactant action that promotes the decomposition and destruction of these substances. We found that the extraction rate of pectin was significantly increased by this method, but we subsequently investigated other surfactants with surfactant effects, namely anionic surfactants, nonionic surfactants, and amphoteric surfactants. As a result, it was found that although each has its own characteristics and its effects are superior or inferior, they all improve the extraction rate. However, since the extraction rate did not necessarily meet the inventor's expectations, further studies were conducted and attention was paid to the aforementioned protopectin. Then, protopectin is transferred to pectin using a compound that has a chelating effect, and the action of acid is used to destroy tissues and cells.
As a result of consideration and consideration of the combined use of the effects of 5-, the present invention was arrived at.

As stated above, an object of the present invention is to provide a novel method for economically and efficiently producing pectin with good quality and performance at a good yield.

The present invention is characterized by adding an acid and a compound having a chelating effect of about 0.01 to 30% by weight to the raw material from a vegetable raw material containing pectin, and extracting pectin by heating. Method for producing pectin 1, and
From a vegetable raw material containing pectin, an acid, a compound having a chelating effect of about 0.01 to 30% by weight relative to the raw material, and about 0.001 to 10% by weight relative to the raw material.
The method for producing pectin is characterized by adding a surfactant (excluding those consisting only of cationic surfactants) and extracting pectin by heating. The effects will be explained in further detail.

-6= The vector used in the present invention/containing plant materials include all fruits (pulp, pericarp), leaves, stems, roots, rhizomes, and all kinds of tubers, including immature ones, or the juice thereof. Although lees are the target, squeezed lees is particularly preferred since it is less commonly used and therefore can be obtained in large quantities. In addition, fruit-thinning products such as mandarin oranges and apples, which are being implemented as a measure to maintain quality and stabilize prices, will also be subject to resource restrictions. However, as mentioned above, pectin is originally a water-insoluble protopectin (
Breakfast Shoten Published on October 30, 1966, 3rd edition, Sugar Handbook, p. 726) exists as a parent body, a macromolecule called Sugar Handbook.For example, as fruits ripen, water-soluble pectin is produced by enzymatic action. The hard fruit gradually becomes soft, and even the mature fruit maintains its shape. The inventor focused on the structure of protopectin, that is, the bonds between carboxyl groups due to metal ions, the bonds due to metal ions via phosphate groups, etc., and found that these bonds could be easily broken industrially to cause the change to pectin. The idea is to use compounds with chelating effects as a way to do this. The compound that has a chelating effect here refers to the Iwanami Physical and Chemical Dictionary (
Iwanami Shoten, published on April 5, 1965, revised 8th edition, No. 34
A compound that forms chelate compounds such as those listed in ``Synthesis of Surfactants and Their Applications,'' by Messrs. Koen and Teramura, Maki Shoten, 1957, 3.
Published on May 20, p. 162), it has a chelating effect that removes metals from molecules containing them and turns them into water-soluble compounds (surfactants: Kodansha, 19''79).
For example, polymerized phosphates, inorganic compounds such as phosphates, and ethylenediamine derivatives, such as ethylenediaminetetraacetate. (commonly known as EDTA),
Examples include organic compounds such as organic acid esters of ethylenediamine/ethylene oxide adducts, hydroxycarboxylic acids and their salts such as tartaric acid and citric acid, and amino acids and their salts such as glutamic acid. It is thought that these compounds having a chelating effect form a metal bond whose bond is cleaved by an acid. Compounds with this chelating effect are based on the history of the plant material, i.e. immature,
It is necessary to adjust the amount by considering maturity, oldness, youngness, dryness, moisture, etc., but the amount added is 0.01 to 30% based on the vegetable material.
Weight % is appropriate. Further, it is essential to use an acid useful for decomposing and destroying plant tissues and cells, and preferred acids include ordinary hydrochloric acid, inorganic acids with sulfuric acid 4, and organic acids such as acetic acid, oxalic acid, and citric acid. Furthermore, depending on the history of the plant material, i.e. its age and degree of dryness, and in the case of fruit, the degree of ripeness and dryness, including the pomace, in other words, the state of tissues and cells, the action of the surfactant may be affected = 9 - Therefore, it facilitates the permeation, swelling, and dissociation of the decomposed extract consisting of acids and compounds with chelating action through plant tissues, between cells, and within the cells, thereby significantly promoting the extraction action of the decomposed extract and increasing the extraction rate. Yes, it is effective. The amount of surfactant used needs to be adjusted depending on the history of the raw material, but the total amount added is 0.00.1 to 10% by weight, preferably 0.0v1 to 10% by weight, based on the raw material. This is because the total amount added includes a mixture of surfactants of the same type or a combination of surfactants of different types.

In addition, the surfactant herein refers to anionic surfactants other than the cationic surfactants, nonionic surfactants, and amphoteric surfactants, each singly or in combination.
However, as mentioned above, when different types of surfactants are used in combination, such as nonionic surfactants and anionic surfactants, nonionic surfactants and amphoteric surfactants, and nonionic surfactants and cationic surfactants. It also includes 10-

Examples of the surfactant are shown below, all of which are applicable to the present invention.

(1) Examples of anionic surfactants include fatty acid salts, alkylbenzenesulfonic acids [(ABS), linear alkylbenzenesulfonates (LAS), alkyl sulfates, mono-olefin sulfonates, alkyl phosphates, dialkyl sulfonates, etc. Succinate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether sulfate, etc.

(2) Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, polyoxyethylene/polyoxypropylene block polymer, Towie/Toka Span (product of Atlas Corporation, USA) type, polyoxy Ethylene glycol fatty acid ester, polyoxyethylene glycerin fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sucrose fatty acid ester, etc.

(3) Examples of amphoteric surfactants include alkylaminocarboxylic acid type surfactants and alkylimidacillin type surfactants.

(4) Examples of cationic surfactants used in combination include quaternary ammonium salts and alkylamine salts.

The pH of the aqueous solution during decomposition and extraction is preferably 1 to 6, more preferably adjusted to pH 2 to 4 using the above-mentioned acid.

The temperature during decomposition and extraction is room temperature to 100C, preferably 40 to 906C. Extraction time is usually 30 minutes to 2
The time is appropriate.

The decomposition extract obtained under the above conditions is filtered to remove decomposition residues, and then further fine suspended matter is removed using a centrifuge or the like, and then concentrated. If there is any precipitated material, it is further removed. Alcohol is added to this purified filtrate to obtain fibrous pectin. The obtained precipitate is purified, dried,
After crushing, quality and performance are measured.

The alcohol has 1 to 5 carbon atoms, specifically hamethyl alcohol, ethyl alcohol, flobyl alcohol,
Isopropyl alcohol is commonly used. Drying is preferably carried out at as low a temperature as possible, i.e. below 906C, preferably under reduced pressure1.Examples and comparative examples of the present invention are shown and explained below, but the technical scope of the present invention is not limited thereto. Of course.

Example 1 Add water to 259 dried and crushed commercially available Onshu mandarin juice lees, heat and stir, and when the liquid temperature reaches '70'C, sodium hexametaphosphate 19 (4 parts by weight relative to the raw material)
was added as an aqueous solution and continued heating and stirring until the liquid temperature reached 80℃.
When the temperature reached 'C, dilute sulfuric acid was added to adjust the pH to 2, and the mixture was stirred at the same temperature for 1 hour to perform decomposition and extraction. The total amount of water to be added is 11 times the amount of raw materials (40 times the amount of water 13 times the amount of raw materials). Next, filtration was performed, and the furnace liquid was further centrifuged in a centrifuge at 3,500 revolutions per minute.
Fine suspended matter and precipitate were removed to obtain purified p liquid. This purified furnace liquid was heated using a rotary evaporator to
Concentrate to about 1/3 volume under reduced pressure at 70°C or lower under the reduced pressure of Ho I (9), centrifuge the resulting concentrated solution again under the same conditions as above, and separate and remove the fine precipitates precipitated by concentration. A purified concentrate was obtained.The content of pectin in this purified concentrate was 5°620γ/ml as galacturonic acid.The method for quantifying this pectin was as per the Fruit Tree Research Institute Report, Series B, No. 5 (1969) Based on the report by Messrs. Ito and Ogaen on pages 63 to 65. Incidentally, γ is 10'g.
It is.

In this case, the yield of pectin per raw material was 7.8%. Note that this converted yield is based on the quantitative value of galacturonic acid mentioned above and the purified concentrate because the yield of the purified concentrate mentioned above is not always constant due to factors such as fluctuations in the concentration rate due to differences in the degree of vacuum during concentration. It is calculated from the yield of the concentrate.

Example 2 Example 1 was carried out using 1 g of sodium tripolyphosphate (4% by weight based on the raw material) in 25 g of the same dried pomace as in Example 1.
Decomposition and extraction were performed in the same manner as above. The pectin content in the purified concentrate is 6,500γ/galacturonic acid.
m7? The converted yield per raw material was 7.9%.

Example 3 1 g of sodium phosphate added to the same dried pomace 259 as in Example 1
(4% by weight based on the raw material) and operated in the same manner as in Example 1 to perform decomposition and extraction. The content of pectin in the purified concentrate is 4.420γ/ml as galacturonic acid.
The conversion yield per raw material was 7.8%.

Example 4 Decomposition and extraction were carried out in the same manner as in Example 1, using the same dried pomace 259 as in Example 1 and using sodium hexametaphosphate 29 (8% by weight based on the raw material). The content of pectin in the purified concentrate is 5.52 as galacturonic acid.
At 0γ/ml, the converted yield per raw material was 8.1%.

Example 5 Decomposition and extraction were performed in the same manner as in Example 1, using 1 g of ethylenediaminetetraacetic acid (4% by weight based on the raw material) on 25 g of the same dried pomace as in Example 1. The content of pectin in the purified concentrate is 5,6 as galacturonic acid.
At 10 γ/durability, the converted yield per raw material was 8.2%.

Example 6 0.5 g of Emar 10 (product of Kao Soap Co., Ltd., lauryl sulfate sodium salt, purity 100%) as an anionic surfactant was added to the same dried pomace 259 as in Example 1.
(2% by weight based on the raw material) was initially added, and when the liquid temperature reached 'i'o'c as in Example 1, sodium hexametaphosphate 19 (4% by weight based on the raw material) was added. The content of pectin in the purified concentrate was 6.320 γ/d as galacturonic acid, and the converted yield per raw material was 8.
, 5chi.

Example 7 25 g of the same dried squeezed lees as in Example 1 was mixed with EMAL 20CM as an anionic surfactant (product of Kao Soap Co., Ltd., polyoxyethylene glycol lauryl ether sulfate, pure content 100%) 0.59 (relative to the raw material). 2% by weight
) and sodium hexametaphosphate 19 (4 for raw material
% by weight) in the same manner as in Example 6 to carry out decomposition extraction. The content of pectin in the purified concentrate is expressed as galacturonic acid6. The converted yield per raw material was 9.0 gamma/ml.

Example Day: 25 g of the same dry squeezed lees as in Example 1 was added with Neugen KA-150 as a nonionic surfactant (product of 17th-Egyo Seiyaku Co., Ltd., polyoxyethylene glycol nonylphenyl ether, purity 100%). 0.5g (2% by weight based on raw materials) and sodium hexametaphosphate 19
(4% by weight based on the raw material) was operated in the same manner as in Example 6 to perform decomposition and extraction. The content of pectin in the purified concentrate was 400 g/g as galacturonic acid, and the conversion yield per raw material was 8.8%.

Example 9 DK Ester F-160 (Daiichi Kogyo Seiyaku Co., Ltd.) as a nonionic surfactant was added to the same dried pomace 259 as in Example 1.
Product, sucrose fatty acid ester, purity 100%) 0.5g
(2% by weight based on the raw material) and sodium hexametaphosphate 19 (4% by weight based on the raw material) in the same manner as in Example 6 to carry out decomposition extraction. The content of pectin in the purified concentrate is 340γ/galacturonic acid.
ml, the conversion yield per raw material was 9.3%.

18- Example 10 The same dry squeezed lees 259 as in Example 1 was mixed with Amhitol 24B (product of Kao Soap Co., Ltd., betaine-type amphoteric surfactant, pure content '100%) as an amphoteric surfactant of 0.59 (raw material). 2 weight) and sodium hexametaphosphate 19
(4% by weight based on the raw material) was operated in the same manner as in Example 6 to perform decomposition and extraction. The pectin content in the purified concentrate was 6,900γ/ml as galacturonic acid.
The conversion yield per raw material was 9.1%.

Example 11 A 4HI surfactant (relative to the raw material) consisting of 0.5 Q of each of Neugen EA150 as a nonionic surfactant and Amhitol 24B as an amphoteric surfactant was added to the same dried pomace 259 as in Example 1. Decomposition and extraction were carried out in the same manner as in Example 6 using sodium hexametaphosphate (4% by weight) and sodium hexametaphosphate (4% by weight relative to the raw material). The content of pectin in the purified concentrate is 4J620γ/ml as galacturonic acid, and the converted yield is 8.4
It was Chi.

Example 12 25 g of the same dried pomace as in Example 1 was mixed with Neugen EA150 as a nonionic surfactant and Emar NC (product of Kao Soap Co., Ltd., polyoxyethylene glycol alkyl phenyl ether sulfate) as an anionic surfactant. , 100% pure) and 0.59% of each (total 4% by weight based on the raw material), and sodium hexametaphosphate 19 (4% by weight based on the raw material). Decomposition and extraction were carried out in the same manner as in Example 6. The content of pectin in the purified concentrate was 5J400γ/vtl as galacturonic acid, and the converted yield was 8.
I was in Section 9.

Example 13 The same dried pomace lees 25Li as in Example 1 was mixed with 0.59 of Neugen EA150 as a nonionic surfactant and Sanizol C-40 (product of Kao Soap Co., Ltd., alkylbenzyl) as a cationic surfactant. Decomposition and extraction were carried out in the same manner as in Example 6 using a surfactant consisting of 1.3 g of dimethylammonium chloride (purity 40%). The content of pectin in the purified concentrate was 4,600 γ/ml as galacturonic acid, and the converted yield was 9.2 cm.

Comparative Example 1 Decomposition and extraction were carried out under the same conditions as in Example 1 without addition. The content of pectin in the purified concentrate was 5,580 γ/d as galacturonic acid, and the converted yield was 5.6 h.

Example 14 For 100 ml of the purified concentrate obtained in the above-mentioned Example 6,
Add 200 d of pure isopropyl alcohol with stirring and pressing down to precipitate pectin, and add the precipitate to '/F.
The precipitate was washed thoroughly with 60% isopropyl alcohol, further washed with pure isopropyl alcohol and then with ethyl ether, and dried under reduced pressure at room temperature to a constant weight to obtain 1.0228 g of almost colorless pectin. The yield was 8°83φ based on the raw material. Regarding this pectin, using a mixed aqueous solution of pH 6 prepared with a 0.4% aqueous solution of sodium hexametaphosphate and a 0.6% aqueous solution of sodium chloride,
3C1bO
, 5'C using an Ostwald viscometer. As a result, the intrinsic viscosity was 3°38, and the pectin grade was calculated to be approximately 150 based on the report by Messrs. Miura and Mizuta published in the Food Research Institute Report, Vol. 14, pp. 6-8 (1959). . Incidentally, pectin grade is also called jelly grade, and is an international standard index that indicates the gelling ability of pectin, that is, its quality.For example, pectin grade 150 is 1 kg of pectin.
It is of a quality that can turn 50 kg of sugar into jelly. Also, P, E, Christensen (P, E, CHR
Food Research (Foo
d Research) Volume 19, No. 163-l 7
The molecular weight was calculated based on the description on page 2 (1,954) and was estimated to be about 72,000. Furthermore, based on the surfactant analysis method (edited by the Surfactant Analysis Study Group, published by Saiwai Shobo on October 1, 1975, first edition, 1st printing, p. 33), Weatherburn (WEA) was used.
The presence or absence of residual lauryl sulfate was investigated using the THERBURN method, but no trace amount of it was detected.

As mentioned above, in order to obtain pectin as a commercial product, concentration is performed to reduce the amount of purified filtrate, and the amount of alcohol (non-solvent) required for precipitation and precipitation of pectin is reduced. Enhances the effects of alcohol. The amount to be used is such that the amount of alcohol is twice the amount of purified concentrate, that is, the system has a volume of 60 to 70 φ
Use it so that it becomes. The resulting pectin precipitate was 60
After washing thoroughly with ~70% alcohol, it is further purified (9
After washing and purifying with alcohol (approximately 0 volume), heat at 70°C.
Dry under reduced pressure as follows. The alcohol used has 1 carbon number
~5 aliphatic primary alcohols, preferably 1 to 3 carbon atoms
Suitable alcohols include methyl alcohol, ethyl alcohol, and propyl alcohol.

Comparative Example 2 0.7076 g of pectin was obtained in the same manner as in Example 14 using 100□7 of the purified concentrate obtained in Comparative Example 1.
As a result of viscosity measurement of the product (yield: 6,07φ), its intrinsic viscosity was estimated to be 2.4'7, pectin grade was approximately 85, and molecular weight was estimated to be approximately 53,000.

Example 15 50 g of refrigerated crushed unshiu mandarin fruit, 400 g of water,
When the temperature of the solution reached 70° C., a solution prepared by dissolving 100 liters of sodium hexametaphosphate (8% by weight based on the raw material) in 100 liters of water was added, and the mixture was heated and stirred. The amount of water added was 500 liters (10 times the amount of the raw materials). Next, when the liquid temperature reached 806C, dilute sulfuric acid was added to adjust the pH to 2, and the mixture was heated and stirred at the same temperature for 1 hour to perform decomposition and extraction. Then, it was subjected to p-filtration, and further centrifuged at a rotation speed of 3,500 revolutions per minute in a centrifuge.
Fine suspended matter and precipitates were removed and purified. The content of pectin in this purified filtrate was 1,6'lJOγ/d as galacturonic acid, and the conversion yield was 1.6%. A precipitate was prepared using 100 tnl of this purified furnace liquid in the same manner as in Example 14. The amount of precipitate was 0.30459 (the yield was 2.9% based on the raw material), and the viscosity was measured, and the intrinsic viscosity was 5°49. , pectin grade is about 250, molecular weight is about 11. It was estimated to be 70,000.

Comparative Example 3 50g of the same refrigerated crushed fruit as in Example 15 and 500ml of water
1 (10 times the amount of the raw material), and decomposition and extraction were performed under the same conditions as in Example 6-15 without adding a compound having a chelating effect. A purified p solution was obtained in the same manner, and pectin was quantified. The result was 1,980 γ/l of galacturonic acid, and the converted yield was 0.
It was 7chi. The precipitation amount is 0.482.
The yield was 1.1% based on the raw material), the intrinsic viscosity was 3.69, the pectin grade was about 170, and the molecular weight was about 790,000.

Patent applicant Mitsuru Koiriki -Ka　-

Claims (1)

[Claims] Extracting pectin from a vegetable raw material containing pectin by adding an acid and a compound having a chelating effect of about 0.01 to 30% by weight with respect to the raw material, and heating the mixture. Method 2 for producing pectin, characterized by: 2. From a vegetable raw material containing pectin, add an acid to it, a compound having a chelating effect of about 0.01 to 30% by weight with respect to the raw material, and about 0.01 to 30% by weight of a compound with respect to the raw material. OO'1~10
A method for producing pectin, which comprises adding a surfactant by weight (excluding those consisting only of cationic surfactants) and extracting pectin by heating.