JPS639521B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an efficient method for producing pectin from vegetable pectin-containing raw materials, and more specifically, the present invention relates to a method for efficiently producing pectin from vegetable raw materials. The present invention relates to a production method in which plant tissue is swollen by adding a quaternary ammonium base to promote the elution of pectin into an extract solution, thereby significantly improving the extraction rate.

Pectin plays an important role in the plant body as a substance present in cell membranes that helps fill the space between cells and thereby maintains plant tissues, such as fruits, leaves, stems, roots, rhizomes, and tubers. It is widely distributed in each part of the plant.

Pectin is added to foods as a gelling agent in the production of jellies, jams, marmalades, etc., as a shape-retention stabilizer in ice cream, sherbet, milk products, etc., as a property stabilizer in soft drinks, and as a water-retaining agent in bread. In addition to being used as an anti-aging agent and a transparent edible coating agent for foods, it has also recently attracted medical attention as a food that lowers serum cholesterol levels, and as a low-calorie food.

Now, as a conventional method for producing pectin, the following method is generally performed. That is, (a) plant materials such as fruit juice lees are crushed, heated to destroy enzymes and prevent decomposition of pectin, and then washed with water and decomposed with acid to turn pectin into water-soluble substances. This pectin extract is filtered using a filtering agent, activated carbon, etc. to remove inert decomposition residues, purified, neutralized, and then concentrated. (b) Alcohol is then added to this purified and concentrated solution to precipitate and precipitate pectin. (c) This precipitate is collected, washed first with hydrous alcohol, then with high-purity alcohol, and dried to obtain pectin, which is a commonly practiced method in industry.

The inventor considered improvements to this general production method and, after examining each step, first focused on the extraction from plant materials in step (a) above. That is, we investigated whether pectin can be extracted sufficiently from plant materials such as fruit juice lees using common manufacturing methods. Since pectin is a high-molecular substance with a molecular weight of approximately 10,000 to 400,000, it is assumed that it would be quite difficult to decompose and extract it from complex plant tissues.

Therefore, it facilitates the penetration of the decomposed extract into the plant cell tissue, and also causes swelling between the cells of the plant tissue and the cells themselves, helping to disperse and destroy them.
As a result of various studies on the addition of quaternary ammonium salts or quaternary ammonium bases with the aim of making it as easy as possible to extract the pectin contained in plants based on both of these effects, we found that a small amount of these The present invention was achieved based on the discovery that the extraction rate of pectin is significantly improved by the addition of .

Note that this quaternary ammonium salt or quaternary ammonium base has extremely high water solubility and is also easily soluble in alcohols, so it can be easily removed, and its use is subject to food safety concerns. There is no need for any concern in this respect.

The vegetable pectin-containing raw materials according to the present invention include mandarin oranges, summer mandarin oranges, oranges, grapefruits, lemons, sabon, etc. of the Rutaceae family, strawberries, plums, pears, apples, peaches, apricots, etc. of the Rosaceae family, grapes of the Vitaceae family, etc. Fruits, leaves, stems, roots, rhizomes, tubers, or juice residues of fruits such as pineapple of the pineapple family and sugar beet of the genus family are widely available. In particular, the juice lees is treated as waste by various fruit juice manufacturers and sugar factories, and despite great efforts and research being made to treat it, some of it is currently used as fertilizer and filler for livestock feed. The reality is that most of them have been discarded.

Therefore, utilizing these as pectin raw materials with relatively high added value has important value from the perspective of resource reuse.

As is clear from the above, an object of the present invention is to provide a new method for producing pure pectin economically and efficiently.

The configuration and effects of the present invention will be explained in detail below.

Any pectin-containing parts of plants can be used as the vegetable pectin-containing raw material used in the present invention, but woody parts of softwoods and hardwoods that require intensive treatment such as peeling, chipping, and cooking can be used. Under these harsh treatment conditions, pectin may decompose, so it is not suitable for treating fruits (including pericarp and pulp), leaves, stems, roots, rhizomes, and tubers of the plants mentioned above, which are low in resin and lignin. Alternatively, these squeezed lees are preferable as a raw material, and the squeezed lees is particularly suitable as a raw material for producing pectin.

In general, water, organic solvents or mixed solvents, acids, alkalis, oxidizing agents, etc. are used to extract components from plant raw materials. Appropriate decomposition and extraction conditions are usually selected after considering properties, chemical resistance, degradability, heat resistance, etc.
In the present invention, the decomposition solution permeates between the cells in the plant tissue to be extracted, and the cells themselves are penetrated between the cells through the action of a surfactant called a quaternary ammonium salt or its base, and the cells are dissociated from each other. By promoting the permeation of the decomposition solution into the cells, we induce cell swelling and destruction to the maximum extent, thereby significantly promoting the extraction action of the decomposition solution and achieving efficient and easy extraction of pectin. This is what I did to get it.

The quaternary ammonium salts or quaternary ammonium bases here belong to cationic surfactants among surfactants, and are exemplified below, all of which are applicable to the present invention. It is. By adding alkali, these quaternary ammonium salts can be The following example shows a salt form, but the same applies to bases.

Alkyl (C number is 8-18), trimethyl ammonium bromide, alkyl (C number is 8-18)
18)・Trimethyl ammonium chloride, alkyl (C number is 8 to 18)・Trimethyl ammonium iodide, alkyl (C number is 8 to 18)・
Dimethyl ammonium bromide, alkyl (C number is 8 to 18), dimethyl ammonium chloride, alkyl (C number is 8 to 18), dimethyl ammonium iodide, methyl diethyl oleylamide ethyl ammonium chloride,
Trimethyl dodecylthiomethyl ammonium chloride, methyl diethyl octylthioethyl ammonium chloride, methyl diethyl octylthioethyl ammonium iodide, trimethyl dodecylmethylaminoethyl ammonium bromide, alkyl (C8-18)・Dimethyl benzyl ammonium chloride, trimethyl benzyl ammonium chloride, alkyl (C8-18) ・pyridinium chloride, alkyl (C8-18) pyridinium bromide, 2-dodecyl isoquinolinium bromide, alkyl (8 to 18 carbon atoms) γ-picolinium bromide, alkyl (8 to 18 carbon atoms) γ-picolinium chloride, and the amount of these quaternary ammonium salts or quaternary ammonium bases to be added by decomposition extraction. Depending on the conditions, i.e., inorganic salts, acids, pH, extraction temperature, extraction time and type of vegetable raw material, 0.001 to 10% by weight of the vegetable raw material, especially 0.01
~5% by weight is desirable. If it is added in an amount of 10% by weight or more, the extract will be markedly colored, and the resulting pectin will also be markedly colored, which is not preferable.

As the inorganic salt to be added, common salt, polymerized phosphate, phosphate, ammonium salt, etc. are used, and these are used to solubilize insoluble pectin.
Organic acids and inorganic acids are used as acids, and mineral acids such as sulfuric acid and hydrochloric acid are usually used, and acetic acid, oxalic acid, etc. are used as organic acids.

The pH of an aqueous solution to which a quaternary ammonium salt or/and a quaternary ammonium base is added when decomposing a vegetable raw material and extracting pectin is preferably 1 to 6, more preferably 2 to 3. Further, the decomposition and extraction time is usually 30 minutes to 2 hours. The extraction temperature is room temperature to 100°C, preferably 40 to 90°C.

By operating under these conditions, the vegetable pectin-containing raw material becomes an amorphous solid, and the pectin is eluted into the decomposition extract. It goes without saying that it is important to stir the raw material and to divide the raw material as finely as possible in order to improve the extraction efficiency during decomposition and extraction. By adding a quaternary ammonium salt or a quaternary ammonium base to which the cationic surfactant belongs, its surface activity against pectin present in the tissue of the plant material to be extracted and present between the cells can be improved. This action not only promotes the permeation of the decomposition extract into and out of the cells, but also causes the cells themselves to swell and actively destroys the cells, compared to conventional decomposition extraction methods. It shows a remarkable decomposition and extraction effect, which is clearly recognized from the following Examples and Comparative Examples. That is, the pectin content in the decomposition extract increases significantly, and the amount of the extract itself also increases, confirming the excellent addition effect of the quaternary ammonium salt or quaternary ammonium base. Furthermore, during filtration, the addition of quaternary ammonium salts or bases significantly changes the state of the extraction residue, and has the side effect of making filtration easier, compared to the case where no addition is made. It is clear that this will be a great advantage in selecting a filter and a filter agent during industrialization. In short, it goes without saying that improved extraction efficiency will have a big positive impact on the effective use of resources. As shown in the Examples, these quaternary ammonium salts or bases were found not to exist in the obtained pectin product, and could be easily and completely removed during the purification process.

Furthermore, since the quaternary ammonium base immediately changes to a quaternary ammonium salt under the action of the acid or inorganic salt coexisting in the decomposition extract, its action and effect are similar to those of the quaternary ammonium salt. There is no problem in viewing them as completely the same.

Examples and comparative examples will be shown and explained below.
Of course, the technical scope of the present invention is not limited to these.

Example 1 Add 1.5 g of water to 500 g of washed apple juice lees, add 1 g of benzyltrimethylammonium chloride (guaranteed reagent manufactured by Hanui Chemical Co., Ltd.) (0.2% by weight based on the raw material), heat, The mixture was stirred, and when the liquid temperature reached 80°C, dilute sulfuric acid was added to adjust the pH to 3, and the mixture was heated and stirred at the same temperature for 1 hour to perform decomposition and extraction. Next, filtration was carried out, and the filtration was carried out more smoothly than in the comparative example. Furthermore, this liquid was centrifuged using a centrifuge at 11,000 revolutions per minute.
After removing fine suspended matter and residue, a dilute aqueous sodium carbonate solution was added to adjust the pH to 6 to obtain a purified liquid.
The yield of this purified liquid was 1400g. In addition, the pectin content in this liquid is expressed as galactyuronic acid.
It was 4850γ/ml. This method for quantifying pectin is based on the Fruit Tree Research Institute Report, Series B, No. 5 (1969), 63.
Based on the report by Messrs. Ito and Tada on pages 65 to 65.
Incidentally, γ is 10 ^-6 g.

As mentioned above, in the case of filtration, coarse impurities are removed using a super-aid in the first filtration, and then the second filtration is carried out.
It is preferable for operation to remove fine insoluble matter by subsequent filtration, and the purified transparent to translucent liquid is treated with an alkali metal hydroxide such as caustic soda, caustic potash, etc., or an alkali metal carbonate, in order to stabilize the quality. For example, it is neutralized with soda carbonate or bicarbonate of soda, but in this case, from the standpoint of stabilizing the quality of pectin, it is appropriate to keep the pH at about 3 to 6.

Example 2 Washed apple juice lees same as Example 1
Add 1.5 g of water to 500 g as in Example 1, add 10 g of benzyltrimethylammonium chloride (guaranteed reagent manufactured by Hanui Chemical Co., Ltd.) (2% by weight based on the raw material), and proceed in the same manner as in Example 1. Decomposition and extraction were performed. The yield of the purified liquid was 1510 g, and the pectin content in this liquid was 3960 γ/ml as galactyuronic acid.

Example 3 500 ml of washed apple juice lees as in Example 1
Add 1.5 g of water in the same manner as in Example 1, and add Cationogen L (registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., alkyltrimethylammonium chloride purity 30%) 85
g (5.1% by weight based on the raw material) was added, and the following operations were performed in the same manner as in Example 1 to perform decomposition and extraction. The yield of purified liquid was 1700g, and the pectin content in this liquid was 3800γ/ml as galactulonic acid.
It was hot.

Example 4 Washing of apple juice lees same as Example 1
Add 1.5 g of water to 500 g in the same manner as in Example 1, and add 100 g of Cationogen H (registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., alkylpiconylium chloride purity 25%) (5% by weight based on the raw materials) and tetra 10 g of polyphosphate sodium salt (2% by weight based on the raw material) was added, and the same procedure as in Example 1 was carried out to perform decomposition and extraction. The yield of the obtained purified liquid was 1650 g, but considerable coloring was observed. The pectin content in this liquid is 4500γ/ml as galactyuronic acid.
It was hot.

Comparative Example 1 Washed apple juice lees same as Example 1
Example 1 shows that 1.5 g of water was added to 500 g, heated, and when the liquid temperature reached 80°C, dilute sulfuric acid was added to adjust the pH to 3, and the decomposition and extraction were performed by heating and stirring at the same temperature for 1 hour. Similar to ~4, but no quaternary ammonium salt or its base or inorganic salt was added. The same procedure was followed, and the yield of purified liquid was 1230 g.
The pectin content in this liquid was 2750 γ/ml as galactyuronic acid. Unlike Examples 1 to 4, the extraction residue was viscous and difficult to filter.

Comparative Example 2 Washed apple juice lees same as Example 1
Add 1.5 g of water and 10 g of tetrapolyphosphate sodium salt (2% by weight based on the raw materials) to 500 g, raise the temperature to 80°C, adjust the pH to 3 with dilute sulfuric acid, and then prepare the following Examples 1 to 1.
4. Operated in the same manner as in Comparative Example 1 to obtain 1256 g of purified liquid. The content of pectin in this liquid was 2700 γ/ml as galactulonic acid. Similar to Comparative Example 1, the extraction residue was viscous and difficult to filter.

Example 5 Add 1.2 g of water to 300 g of washed lemon lees and add benzyltrimethylammonium chloride.
Add 0.3g (0.1% by weight based on the raw material), heat, and when the liquid temperature reaches 80℃, add dilute sulfuric acid to adjust the pH.
2, and then heated and stirred at the same temperature for 1 hour to perform decomposition and extraction. Next, filtration, purification, filtration, and neutralization were performed. The yield after this purification was 1460 g, and the pectin content therein was 2400 γ/ml as galactulonic acid.

Comparative Example 3 300g of washed lemon lees same as Example 5
1.2 liters of water was added to the solution, heated and stirred without adding any inorganic salt, quaternary ammonium salt or its base, and when the liquid temperature reached 80°C, dilute sulfuric acid was added to adjust the pH to 2. The following operations were carried out in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 2, and the yield of purified liquid was 1260 g, and the amount of pectin contained therein was 2270 γ/ml as galactyuronic acid.

Example 6 The purified filtrate obtained in Example 2 above was purified under a reduced pressure of 50 mm/Hg using a rotary evaporator.
It was concentrated at 60° C., and the resulting concentrated solution was centrifuged again to remove the generated suspended matter for purification. 200ml of isopropyl alcohol for 100g of this purified liquid
was poured under stirring to precipitate pectin, collect the precipitate, wash the precipitate with 60% isopropyl alcohol, further wash with 87% isopropyl alcohol, then ethyl ether, dry under reduced pressure at room temperature to a constant volume, and remove the precipitate. 0.998 g of white pectin was obtained. About this pectin 0.4 of sodium hexametaphosphate
Using a mixed aqueous solution of PH6 adjusted with a 0.6% aqueous solution of sodium chloride and a 0.6% aqueous solution of sodium chloride, the viscosity was measured at 30°±0.05°C for each solution of 0.2, 0.15, 0.1 and 0.05% (g/ml). An Ostwald viscometer was used as the viscometer. As a result, the intrinsic viscosity was determined to be 3.47, and the pectin grade was approximately 155, based on the report by Messrs. Miura and Mizuta in Food Research Institute Report, Vol. 14, pp. 6-8 (1959). Also, P. E. Christensen: Food Squirrel, (PECHR ISTENSEN:
Food Res.) 19 , 163-172 (1954), its molecular weight was estimated to be about 74,000. Furthermore, an infrared absorption spectrum was taken to confirm that it was pectin, and that there was no trace of quaternary ammonium salt.

As mentioned above, in order to obtain the final product pectin, the purified liquid is first concentrated under reduced pressure.This concentration reduces the amount of purified liquid and the subsequent precipitation of pectin with alcohol, reducing the amount of alcohol required for precipitation. This is to improve the effect of pectin as a precipitant, and to precipitate pectin from a purified solution,
Precipitation agent (non-solvent) for 1 part of concentrated purified liquid
1 to 2 parts of 60 to 70% by volume alcohol is used as the alcohol. The resulting pectin precipitation is again
A high-purity product can be obtained by washing with 60-70% alcohol by volume, further washing and purifying with alcohol of high purity (approximately 90% by volume or more), and then drying under reduced pressure at 90°C or less. . Further, suitable alcohols to be used are aliphatic primary alcohols having 1 to 5 carbon atoms, preferably methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol, which are aliphatic primary alcohols having 1 to 3 carbon atoms.

Example 7 After concentrating the purified liquid obtained in Example 5, it was centrifuged in the same manner as in Example 6, pectin was precipitated with isopropyl alcohol, and as a result of washing, purifying, and drying, a white product was obtained. pectin 1848
I got g. The viscosity of this product was measured in the same manner as in Example 6. As a result, the intrinsic viscosity was 2.75, the pectin grade was approximately 110, and the molecular weight was estimated to be approximately 59,000. Furthermore, an infrared absorption spectrum of this pectin was taken, and it was confirmed that it was pectin, and that no quaternary ammonium salt remained.

Example 8 Add 850 ml of water to 50 g of dried sugar beet (beet, sugar beet) lees, add 0.105 g of benzyltrimethylammonium chloride (0.21% by weight based on the raw material), heat and stir, and carry out the following procedures. The pH was adjusted to 3 in the same manner as in Example 1, and decomposition and extraction were carried out, followed by centrifugation after filtration, and the pH was adjusted to 6 to obtain 550 g of a purified liquid. The pectin content in this liquid was 3860 γ/ml as galactulonic acid.

Example 9 850 ml of water was added to 50 g of the same dried sugar beet lees as in Example 8, and to this was added 0.24 g of benzyltrimethylammonium chloride (based on the raw material).
0.48% by weight) was added, heated and stirred until the liquid temperature was 80℃.
When the pH reached 2g, 2g of sodium hexametaphosphate (4% by weight based on the raw material) and dilute sulfuric acid were added to adjust the pH to 2.
g was obtained, and the pectin content in this liquid was 6080 γ/ml as galactyuronic acid.

Example 10 Add 850 ml of water to 50 g of the same dried sugar beet lees as in Example 8, and add cation
Add 3.3g of L (1.88% by weight based on the raw materials), heat and stir, and when the liquid temperature reaches 80℃, add 2g of salt.
(4% by weight based on raw materials) and add dilute sulfuric acid to pH
2, and the following procedure was carried out in the same manner as in Example 1, and the purified liquid was
540 g was obtained, and the pectin content in this liquid was 6100 γ/ml as galactulonic acid.

Comparative Example 4 850 ml of water was added to 50 g of the same dried sugar beet lees as in Example 8, heated and stirred until the liquid temperature reached 80
When the temperature reached ℃, dilute sulfuric acid was added to adjust the pH to 3, followed by heating and stirring at the same temperature for 1 hour to perform decomposition and extraction, except that quaternary ammonium salts or inorganic No salt was added. The yield of the obtained purified liquid was 500g, and the pectin content in this liquid was 3240γ/ml as galactyuronic acid.
It was hot. Compared to Examples 8 and 9, it was difficult to pass.

Example 11 Add water to 100g of squeezed lees of Kishu Unshu mandarin orange produced in Arita
Add 300 ml of alkylbenzyl dimethyl ammonium chloride (manufactured by Meisei Chemical Co., Ltd., purity 40%) to this, add 11 g (4.4% by weight based on the raw material), heat and stir, and proceed as in Example 1. 400 g of purified liquid was obtained, and the pectin content in this liquid was 8120 γ/ml as galactyuronic acid, and the total amount of pectin in the liquid was about 3.2 g. 100 g of this purified liquid was centrifuged to remove suspended matter again, and the same procedure as in Example 6 was carried out to obtain 0.508 g of yellowish white pectin. Regarding this, the viscosity was measured in the same manner as in Example 6, and the results showed that the intrinsic viscosity (30°C)
is 4.16 and the pectin grade is about 190,
Its molecular weight was estimated to be about 88,000.

Comparative Example 5 300 ml of water was added to 100 g of squeezed lees of the same Kishu Satsuma mandarin orange produced in Arita as in Example 11, and the mixture was heated and stirred without adding quaternary ammonium salt or its base or inorganic salt. Repeat the same procedure and use the purified solution.
Obtained 320g. The content of pectin in the liquid is
The total amount of pectin in the liquid was approximately 2.9 g at 9100 γ/ml.

Claims (1)

[Scope of Claims] 1. A method for producing pectin in which pectin is extracted by adding an aqueous solution of an acid or/and an inorganic salt to a vegetable pectin-containing raw material and heating it, in which a quaternary ammonium salt or/and which belongs to a cationic surfactant is added. and a method for producing pectin, which comprises adding a quaternary ammonium base to the aqueous solution. 2. In the method for producing pectin according to claim 1, the amount of the quaternary ammonium salt or/and quaternary ammonium base added is 0.001 to 10% by weight of the vegetable pectin-containing raw material. Manufacturing method. 3. In the method for producing pectin according to claim 1 or 2, the pH value of the aqueous solution for extracting the pectin to which the quaternary ammonium salt or/and quaternary ammonium base is added is 1 to 1. 6. Method for producing pectin.