JPH08188593A - Extraction and recovery of hesperidin contained in citrus fruits - Google Patents

Abstract

PURPOSE: To provide a method for efficiently extracting hesperidin from squeezed lees of tangerine and a method for recovering hesperidin from an extracted solution of hesperidin. CONSTITUTION: Squeezed lees of a citrus fruit is adjusted to pH11.5 to pH12.5 by adding an alkaline earth metal compound such as calcium hydroxide using a pH adjustor and mixed under stirring after pH adjustment. The stirred mixture is squeezed under a prescribed pressure and the pressed liquid obtained by squeezing centrifuged to give an extracted solution of hesperidin. The prepared extracted solution of hesperidin is adjusted to pH5.0 to pH5.5, heat-treated once and centrifuged to recover hesperidin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for extracting and recovering hesperidin contained in citrus fruits.

[0002]

BACKGROUND ART Wenzhou mandarin oranges are one of the major fruits in Japan.
However, there are cases where it is peeled off and eaten as it is, and when it is squeezed and served as a beverage. By the way, when you squeeze Unshu mandarin oranges, squeezed lees always occur. This squeezed lees, except that part of it is used for livestock feed, etc.
In general, it is currently disposed of after being dried.

The squeezing liquid (secondary squeezing liquid) obtained by the liming and squeezing treatments, which are carried out as a pretreatment for the drying step of the squeezed lees, is partially concentrated and used as a raw material for fermentation as citrus molasses. Most of them are discarded.

[0004]

However, squeezed lees, including secondary squeezed juice, have vitamin P activity and are used as a food fortifying agent and a cold medicine compound. It contains a large amount of hesperidin, which has been reported to have new pharmacological actions such as antihypertensive action and antiallergic action. Therefore, simply discarding such squeezed meal is a waste of resources.

By the way, as a method for extracting hesperidin contained in Satsuma mandarin orange juice cake, dried juice cake (dried skin) produced as a by-product of fruit juice processing is treated with sodium hydroxide and extracted. The method, the so-called alkali extraction method, is generally known. However, this method is inefficient because the squeezed lees are dried in advance, and moreover, since many impurities coexist in the obtained extract, the yield is low and it is difficult to dispose of the discharged residue. Therefore, it has not been put to practical use industrially.

In view of such circumstances, the present invention provides a method for extracting hesperidin capable of efficiently extracting hesperidin from Mandarin orange juice cake and a method for recovering hesperidin capable of efficiently recovering hesperidin from the hesperidin extract. It is intended to be provided.

[0007]

The invention according to claim 1 (hereinafter,
The method for extracting hesperidin according to the "first invention" is selected from the group consisting of citrus juice dregs and alkaline earth metal hydroxides, carbonates, sulfates, nitrates, lactates, chlorides and the like. The pH of 11.5-12.5 by adding at least one alkaline earth metal compound and a pH adjuster, the step of stirring and mixing after pH adjustment, and the stirring mixture at a predetermined pressure. The constitution was provided with a step of squeezing and a step of centrifuging the squeezed liquid obtained by squeezing to obtain a hesperidin extract.

In the above construction, the alkaline earth metal compound is not particularly limited, but for example, calcium hydroxide, calcium chloride, calcium carbonate, calcium lactate, barium chloride, magnesium hydroxide, magnesium chloride, magnesium sulfate, magnesium nitrate. Etc. Examples of pH adjusters include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide.

However, in consideration of safety as a food material and a raw material for medicines, economy, work efficiency, etc., a method of combining calcium hydroxide with sodium hydroxide or potassium hydroxide is effective. The pH of the squeezed lees is 11.
It is adjusted to 5 to 12.5, but the vicinity of 12 is most preferable. That is, when the pH of the squeezed lees is less than 11.5, hesperidin cannot be sufficiently extracted, and the pH is 12.5.
Even if it exceeds, the extraction efficiency of hesperidin will not be further improved.

Incidentally, when calcium hydroxide is used as the alkaline earth metal compound, the addition amount thereof is preferably about 0.5 to 1.0% by weight based on the squeezed lees. The method for recovering hesperidin according to the invention of claim 2 (hereinafter, referred to as “second invention”) is a method in which the hesperidin extract obtained in the first invention is adjusted to pH 5.0 to 5.5 and then once heated. The step of treating, the step of dispersing the first centrifugal sludge obtained by centrifuging the heat-treated extract in a predetermined amount of water, the step of centrifuging the aqueous dispersion of the first centrifugal sludge and the second centrifugation The configuration includes a step of obtaining sludge and a step of drying the second centrifugal sludge.

In the above-mentioned constitution, first, the pH of the hesperidin extract may be adjusted to an acidic range of 7.0 or less, but if the pH is lower than 5.0, the purity of the recovered hesperidin is lowered and the pH is lowered. When it exceeds 5.5, the tendency for the recovery rate of hesperidin to decrease becomes stronger, and the pH is 5.0 to 5.5.
Adjust to. The pH of the hesperidin extract can be adjusted by adding an acid such as hydrochloric acid.

Further, the heating temperature after pH adjustment is 60 ° C.
The above is preferable, and about 70 degreeC is especially preferable. That is, when the temperature is lower than 60 ° C, the hesperidin recovery rate decreases. It should be noted that the recovery of hesperidin does not improve even if it is heated above 75 ° C and further. The heat-treated extract is preferably cooled once to around 20 ° C. That is, the hesperidin recovery rate is not particularly affected by cooling, but cooling to around 20 ° C. is preferable in terms of operability.

Further, the recovery rate of hesperidin can be arbitrarily adjusted by adjusting the heating temperature and the holding time until the centrifugation. The method for recovering hesperidin according to the invention of claim 3 (hereinafter, referred to as “third invention”) is the method for recovering the hesperidin extract obtained in the first invention by pH
After adjusting to 5.0 to 5.5, the step of once heating, the supernatant obtained by centrifuging the heat-treated extract is passed through a column packed with an adsorbent, and hesperidin in the supernatant is added. Is adsorbed on the adsorbent, a step of eluting hesperidin adsorbed on the adsorbent with a solvent, and a step of concentrating the eluate.

In the above structure, the adsorbent is not particularly limited, but examples thereof include styrene DVB (divinylbenzene) -based, acrylic DVB-based, and phenol-based synthetic adsorbent resins. The solvent is not particularly limited, but examples thereof include alcohols such as ethanol and isopropyl alcohol, and ethanol is particularly preferable in consideration of safety.

When ethanol is used as a solvent, if it is 30% by weight or more, there is no particular problem, but 50 to 50% by weight.
It is preferably used as an aqueous solution of about 75% by weight.

[0016]

According to the constitution of the first aspect of the present invention, it is a cause that the conventional extraction efficiency contained in the squeezed lees is lowered and that pectin which is a contaminant is alkaline earth such as calcium pectinate or magnesium pectate. It is considered that hesperidin is easily extracted because it is converted into a metal salt and removed.

According to the configuration of the second invention, the hesperidin extract obtained by the extraction method of the first invention is efficiently and
Hesperidin can be recovered. According to the configuration of the third invention, the hesperidin concentrated liquid having a high concentration can be efficiently recovered from the hesperidin extract obtained by the extraction method of the first invention.

[0018]

[First process]

1-As shown in FIG. 1, 200 kg of Satsuma mandarin fruit was squeezed to obtain 100 kg of juice and 100 kg of squeezed lees.
The obtained juice residue contained 80.2% of water and 1.08% of hesperidin.

1- To 100 kg of this squeezed lees, 0.75 kg of calcium hydroxide was added, and 19.25 kg of a 4.3% sodium hydroxide solution was further added to adjust the pH to 12. 1- In this state, after stirring and mixing for 30 minutes, 30-
It was pressed at a pressure of 40 kg / cm ² .

1- Press the squeezed liquid to 100 mesh (150
(μm) and then subjected to centrifugation to obtain a hesperidin extract as a supernatant. The total amount of hesperidin contained in the obtained hesperidin extract is
64.1 of hesperidin contained in 100 kg of squeezed lees
%Met. [Second Process] 2-As shown in FIG. 2, 1.4 liters of 12N hydrochloric acid was added to the hesperidin extract obtained in the first process to adjust the pH to 5.0, followed by heating (70 ° C.) and cooling. (20
C) was continuously performed to obtain a cooling liquid.

2- The cooling liquid is centrifuged to obtain 4.5 kg of the first centrifugal sludge as a precipitate fraction, and 65
A supernatant of kg was obtained. The total amount of hesperidin of 4.5 kg of the first centrifugal sludge was 30.4% of hesperidin contained in 100 kg of squeezed lees. Also, 65
The total amount of hesperidin contained in the supernatant of kg is 10
It was 31.1% of hesperidin contained in 0 kg of squeezed lees.

2-4.5 kg of the centrifugal sludge obtained by separation was washed with 60 liters of water, and then 2.3 kg of a second centrifugal sludge which had been subjected to centrifugal separation treatment was obtained.
The total amount of hesperidin contained in 2.3 kg of the second centrifugal sludge was 27.7% of hesperidin contained in 100 kg of squeezed lees. 2- Dry 2.3 kg of the second centrifugal sludge to 0.4
2 kg of crude hesperidin was obtained. The crude hesperidin obtained had a hesperidin content of 70.0%, and the total amount of hesperidin in the crude hesperidin was 100 kg.
It was 27.1% of the hesperidin contained in the squeezed lees.

[Third Process] 3-As shown in FIG. 2, 65 kg of the supernatant liquid obtained in the above step 2 is passed through a column packed with a synthetic adsorption resin as an adsorbent, and the supernatant liquid Hesperidin was adsorbed on a synthetic adsorption resin. 3-synthesized synthetic resin with hesperidin
After washing with 0 liter of water, hesperidin was eluted with 70% (W / W) ethanol to obtain 80 liter of eluate. The total amount of hesperidin contained in the eluate was 28.0% of hesperidin contained in 100 kg of squeezed lees.

3-concentrate the obtained eluate to 2.9
7 kg of hesperidin concentrate was obtained. The hesperidin content in the hesperidin concentrated solution was 10.0%, and the total amount of hesperidin contained in the hesperidin concentrated solution was 27.27 with hesperidin contained in the squeezed lees being 100%.
5%. The extraction and recovery conditions, including the amount of calcium hydroxide added when obtaining the hesperidin extract, were determined as follows.

In other words, Satsuma mandarin juice cake (water content 84.
2%, hesperidin content 0.84%) 1000 g of calcium hydroxide in the range of 0 (no addition) to 1.0% by weight, in increments of 0.25% by weight, and 1.0
The pH is adjusted to 12 by adding 0.5% by weight in the range of 0.5% to 2.0% by weight and further adding 1N sodium hydroxide solution or potassium hydroxide solution, and the total amount is adjusted to 1200 g with water. Prepared. In this state, the mixture was stirred and mixed for 30 minutes and then pressed (squeezed).

Next, the obtained squeezed liquid was filtered through a 100-mesh (150 μm) sieve, and then the filtrate was subjected to a centrifugal separation treatment (10000 rpm, 10 minutes) to obtain a supernatant as a hesperidin extract. Then, the amount of hesperidin extract, the hesperidin content and the hesperidin extraction rate are shown in Table 1 (pH adjuster: sodium hydroxide) and Table 2.
(PH adjuster: potassium hydroxide).

[0027]

[Table 1]

[0028]

[Table 2]

As shown in Tables 1 and 2, the addition ratio of calcium hydroxide was 0.
It was found that the hesperidin extraction rate was high in the range of 5 to 1.0% by weight. In particular, it was revealed that the extraction can be performed most efficiently when adding 0.75% by weight of calcium hydroxide. Therefore, 0.75% by weight of calcium hydroxide was added as described above.

Comparative Example 1 A hesperidin extract was obtained in the same manner as in Example 1 except that calcium hydroxide was not added at all and only sodium hydroxide was added to 100 kg of squeezed lees for extraction. However, a large amount of impurities were mixed in the hesperidin extract, and the total amount of hesperidin contained in the hesperidin extract was about 10% of the total amount contained in 100 kg of squeezed lees.

(Example 2) 100 mmol / kg of calcium hydroxide (7.5 g) and calcium chloride (dihydrate, 14.3%) per 1000 g of Satsuma mandarin orange juice cake (hesperidin content 0.96%). 7g), calcium carbonate (1
0.0 g), barium chloride (dihydrate, 24.4 g) and magnesium nitrate (hexahydrate, 24.6 g), respectively, and further adjust the pH to 12 by adding sodium hydroxide solution. Together with water, the total amount is 12
It was adjusted to 00 g. In this state, the mixture was stirred and mixed for 30 minutes and then pressed (squeezed).

Next, the obtained squeezed liquid was filtered through a 100-mesh (150 μm) sieve, and then the filtrate was centrifuged (10000 rpm, 10 minutes) to obtain a supernatant as a hesperidin extract. Table 3 shows the hesperidin content and the hesperidin extraction rate of the extracts obtained by using the respective alkaline earth metal compounds as described above, together with the case of no addition.

[0033]

[Table 3]

As shown in Table 3, the extraction ratios of all the compounds were significantly improved as compared with the additive containing no alkaline earth metal compound. In particular, the addition of calcium hydroxide, calcium chloride and barium chloride markedly improved the extraction effect of heshelidine.

Example 3 Calcium chloride (dihydrate) in an amount of 0.25% by weight in the range of 0% by weight to 1.00% by weight per 1000 g of Satsuma mandarin orange juice cake (hesperidin content 1.17%). %, And 1.00% by weight to 2.
Add 50% by weight in increments of 0.50% by weight and add sodium hydroxide solution to adjust the pH to 1
The hesperidin extract was obtained in the same manner as in Example 2 except that the amount was adjusted to 2. The hesperidin content and hesperidin extraction rate of the obtained hesperidin extract were measured, and the results are shown in Table 4.

[0036]

[Table 4]

As shown in Table 4, the extraction rate of hesperidin is 0.75% by weight to 2.0% by the amount of calcium chloride added.
It increased in the range of 0% by weight. In particular, when 1.50% by weight of calcium chloride was added, that is, when the concentration was about 100 millimoles per 1 kg of squeezed lees, extraction was most efficient. That is, it was found that the addition ratio of the alkaline earth metal compound is optimally about 100 millimoles per 1000 g of Satsuma mandarin orange cake regardless of the type of the compound.

(Example 4) 14.7 g of calcium chloride (dihydrate) corresponding to 100 mmol per 1000 g of Satsuma mandarin orange cake (hesperidin content 0.96%)
Is added, and the pH is adjusted to 10.0 to 1 with sodium hydroxide solution.
A hesperidin extract was obtained in the same manner as in Example 2 except that samples having different pH values in 0.5 increments in the range of 3.0 were prepared.

The hesperidin content rate and the hesperidin extraction rate of the obtained hesperidin extract were measured,
The results are shown in Table 5.

[0040]

[Table 5]

As shown in Table 5, when the pH is adjusted to the range of 11 to 13, the extraction rate becomes high, and particularly pH 11.5.
With the above, it was possible to extract efficiently. Then, in consideration of economic efficiency, it was found that it is most preferable to adjust the pH to 11.5-12.5.

Example 5 7.5 g of calcium hydroxide corresponding to 100 mmol was added to 1000 g of mandarin orange juice cake (hesperidin content 1.07%), and 6N sodium hydroxide solution was further added. PH
An extract was obtained in the same manner as in Example 2 except that the concentration was adjusted to 12. Subsequently, the extract was adjusted to pH 4.0 to 6.5 with hydrochloric acid.
Samples were obtained in which the pH was changed in steps of 0.5. Then, each sample was heated to 70 ° C. to precipitate hesperidin, and then immediately centrifuged at 20 ° C. for 5 minutes (10,000 rpm), and the obtained precipitate was dried to recover crude hesperidin. The crude hesperidin thus recovered was examined for purity and recovery rate, and the results are shown in Table 6.

[0043]

[Table 6]

As shown in Table 6, the recovery rate of hesperidin was not so different in the range of pH 4.0 to 6.5, but the purity of the crude hesperidin obtained was the highest in the range of pH 5.0 to 5.5.

(Example 6) To the extract obtained in the same manner as in Example 5, hydrochloric acid was added to adjust the pH to 5.0, and 40 to 8
Crude hesperidin was recovered in the same manner as in Example 5, except that the heating treatment was carried out by changing the heating temperature in steps of 10 ° C to 0 ° C. The purity and the recovery rate of the crude hesperidin thus recovered are examined, and the purity and the recovery rate of the crude hesperidin obtained by immediately centrifuging at room temperature after pH adjustment are shown in Table 7.

[0046]

[Table 7]

As shown in Table 7, the purity and the recovery rate of the obtained hesperidin were improved by the heat treatment, especially as the temperature became higher. Then, at 70 ° C. or higher, the value became almost constant.

[0048]

Since the method for extracting hesperidin according to the first aspect of the invention is configured as described above, it is possible to efficiently obtain a hesperidin extract containing hesperidin at a high concentration. The method for recovering hesperidin according to the second invention can efficiently recover highly pure hesperidin from the hesperidin extract obtained by the extraction method according to the first invention in a short time.

In the method for recovering hesperidin according to the third aspect of the present invention, a high-concentration hesperidin concentrate can be efficiently obtained in a short time from the hesperidin extract obtained by the extraction method of the first aspect. The obtained hesperidin concentrated liquid can be effectively used as a functional material.

[Brief description of drawings]

FIG. 1 is a flow chart showing an embodiment of a method for extracting hesperidin according to the present invention.

FIG. 2 is a flow chart showing an embodiment of a method for recovering hesperidin according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C07B 63/04 7419-4H (72) Inventor Shigeru Ayano 4-2-61 Sekido, Wakayama City Grand Heights Sekido 310 (72) Inventor Yoshihiko Ozaki 1501-2 Tsubo, Shimotsu-cho, Seaweed-gun, Wakayama Prefecture 72-72 Keiji Hatake 5-48 Wakagawa-cho, Wakayama City (72) Inventor Kazuyuki Maruyama 168 Onoda, Kainan-shi, Wakayama Prefecture

Claims (3)

[Claims] 1. At least one alkaline earth metal compound selected from the group consisting of hydroxides, carbonates, sulfates, nitrates, lactates and chlorides of alkaline earth metals in citrus juice dregs. And pH adjuster are added to adjust the pH to 11.5-1.
A step of adjusting to 2.5, a step of stirring and mixing after pH adjustment,
A method for extracting hesperidin, which comprises a step of squeezing the stirred mixture at a predetermined pressure and a step of centrifuging the squeezed liquid obtained by the squeezing to obtain a hesperidin extract. 2. A process of adjusting the pH of the hesperidin extract obtained by the extraction method of claim 1 to pH 5.0 to 5.5, heating it once, and centrifuging the heat-treated extract. The step of dispersing the first centrifugal sludge in a predetermined amount of water, the second dispersion of the first centrifugal sludge in an aqueous dispersion
The method for recovering hesperidin, comprising the steps of obtaining the centrifugal sludge and drying the second centrifugal sludge. 3. A step of heating the hesperidin extract obtained by the extraction method of claim 1 after adjusting the pH to 5.0 to 5.5, and then centrifuging the heat-treated extract. Passing the supernatant liquid through a column packed with an adsorbent, and adsorbing hesperidin in the supernatant liquid to the adsorbent,
A method of recovering hesperidin comprising a step of eluting hesperidin adsorbed on an adsorbent with a solvent and a step of concentrating the eluate.