JPS60829A - Regeneration of active carbon for purifying citrus juice - Google Patents

Abstract

PURPOSE:To obtain active carbon having sufficient activity for reutilization with a simple pocedure by heating active carbon used previously for adsorption of flavonoids together with aq. soln. of citric acid, malic acid, or tartaric acid then separating the active carbon. CONSTITUTION:Active carbon used previously for adsorption of flavonoids in a process for treating fruit juice of citrus fruit or soup obtd. from the lees of citrus fruit with active carbon for purification, is heated together with aq, soln. of citric acid, malic acid, or tartaric acid and then separated. The concn. of the aq. soln. of said acid is adjusted to 0.3-10% and the treating temp. is preferred to be 50-100 deg.C and the amt. of the acid soln. to be added to the active carbon is 2-10 times weight as compared to the weight of the active carbon. Active carbon having sufficient activity for reutilizations is thus obtd. by this simple procedure.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for regenerating activated carbon for purifying citrus juice.

That is, the present invention is a method for purifying citrus fruit juice or fruit juice obtained from its juice residue by treating it with activated carbon, which involves heating the reused activated carbon to zero with a water bath solution of citric acid, malic acid, or tartaric acid. A method for regenerating activated carbon for purifying citrus juice, which is characterized by - This can cause strong bitterness, crystal precipitation, and turbidity in fruit drinks that use this fruit juice, so when producing fruit juice, there are various ways to avoid mixing it with fruit juice or to remove it. For example, when extracting juice, the number of angular insects between the fruit juice part and the naringin-containing part should be minimized, and the juice part should be quickly removed from the tissue.
In order to
In addition, a method is used in which the fruit juice is extracted from the system by pressing in one operation. A method of treating fruit juice with a combination of ion-exchange resin and activated carbon, and a method of using a flavonoid-degrading enzyme, etc.75 (including methods disclosed in US Special Review No. 310,797), etc. The pH of the fruit juice or pericarp liquid obtained from the pericarp was adjusted to pH, ?, !r ~ 7.0, so- using activated carbon.
A method of processing using gθC is known.

The present inventors have conducted research on the purification of citrus juice using activated carbon, and have found that the process is extremely simple to operate compared to conventional ion exchange methods or flavonoid-degrading enzyme methods. It has been confirmed that the process can be carried out easily, and requires only a small amount of auxiliary materials, equipment, and costs, making it industrially advantageous. The quality of fruit juice purified by treatment with activated carbon differs from that of the original fruit juice in terms of sugar content,
Compared to the degree of decrease in the content of organic acids and amino nitrogen, the rate of decrease in flavonoids is much greater (without impairing the flavor of the fruit juice).

This indicates that undesirable components such as bitterness have been removed. (Thus, according to this method of treatment with activated carbon, it is generally possible to produce a mild and good flavor even in unripe fruits that are prematurely ripe or unsuitable fruits that have been damaged by cold and have lost their market value because they yield only bitter juice.) It goes without saying that it would be more convenient if the activated carbon used to remove flavonoids could be recovered and reactivated and used repeatedly. This is the most important point that affects the economic efficiency of the industrial implementation of the method used, and as a result of intensive research on this point, the present inventors have found that -i. obtained the knowledge that activated carbon with sufficient activity for reuse can be obtained by an extremely simple operation of heating activated carbon with a water bath solution of citric acid, malic acid, or tartaric acid and then separating the activated carbon, Based on this, the present invention was completed.

In the present invention, in the purification of fruit juice or pericarp liquid obtained from pericarp, activated carbon that has been used once is regenerated by the following method and used repeatedly. Add and mix an appropriate amount of a water bath solution of citric acid, malic acid, or tartaric acid with an appropriate concentration to the collected used activated carbon to be regenerated, heat it to an appropriate temperature in a heating pot, for example, and hold it for an appropriate time. For example/-A After stirring for 0 minutes at this temperature, the activated carbon is separated from an aqueous solution of citric acid, malic acid, or tartaric acid, for example by filtration through an Oliver filter or by a centrifuge.0 The citric acid used here , the concentration of malic acid, 'f, or tartaric acid in the water bath solution,
The range of temperature and amount added affects regeneration titer, regeneration time, and economical efficiency, so it is preferable to select them appropriately.

For example, the concentration of the aqueous solution of the above acid is 0. ．． If it is lower than 34, the decolorizing power and flavonoid removal power will not be recovered sufficiently, and
If Qe/J is exceeded, the acid adsorbed on the activated carbon becomes concentrated (transferred to the processing solution) and the economical efficiency becomes poor. Therefore, it is preferable to set the concentration of the aqueous acid solution to 0.3 to /Q4.

Furthermore, if the treatment temperature is below SO'6, the recovery of activated carbon titer is weak and special equipment is required for the Oliver filter, so the treatment temperature is preferably SO to 1OOC. The ability to sufficiently recover the titer of activated carbon by heating in the range of SO to 100C; a high temperature of 90 to 700C is preferable because the treatment time is short. It is desirable that conditions such as being able to separate activated carbon and acid bath liquid in a short time using an Orinoku-filter are met, and of course that the adsorption power of activated carbon can be restored. , the appropriate range is 4 to 70 times the amount.
After washing with water several times, the water is removed by filtration or centrifugation and used again for the flavonoid removal step.

The present invention does not require high-temperature calcination operations, which are considered essential for general activated carbon regeneration, and uses citric acid, sulfonic acid, and tartaric acid, which are designated as food additives, so it does not require the use of other chemicals. Differently, this recycled activated carbon is
There is no problem even if the water washing step is omitted and the product is used as it is for the next flavonoid removal treatment. In addition, the regeneration method according to the present invention does not require the construction and installation of a special regeneration plant, and the present invention can be fully implemented with the equipment of general food and fruit juice factories, so the present invention is a very advantageous method. It is.

Next, the present invention will be explained with reference to examples.

Example 1 [Reuse of activated carbon when producing secondary fruit juice [fruit syrup] from the squeezed lees of the mandarin oranges] The remaining squeezed lees XO
Add slaked lime Otsu 9, which meets the standards for food additives, to O sand to make approximately I
After mixing and reacting for 0 minutes (so-called liming), the mixture is squeezed using a screw press.

Ky's secondary fruit juice and cake obtained approximately 1000 Kf. After removing floating pulp from this secondary fruit juice using a scheming type centrifuge, it was placed in a stainless steel double boiler equipped with a stirrer and rapidly heated to 9I' After maintaining the temperature at -100C for 15 minutes to sufficiently precipitate sludge containing calcium salt as a living body, powdered activated carbon 27 sand was added, and stirring was continued for to minutes at 93 to 1 OOC. This was separated using an Oliver filter, and the used activated carbon (water-containing material containing about 60% of water) g3 and fruit juice were obtained.

The fruit juice obtained by filtration is further added with diatomaceous earth as an f-perexcitant, and subjected to f-filtration using a foliar pressurized FA machine to produce a transparent syrup ["Decarbonized Labonoid Fruit Juice (1)" in Table 1 shown below] The corresponding 'JgokEy was obtained. This syrup was concentrated using a forced circulation vacuum evaporator to obtain a thick syrup of Br1x 70″' [rBx in Table 1].

Equivalent to 70% flavonoid-free fruit juice (1)] 100K
I got 1. This syrup is a pale orange transparent viscous liquid with a mild sweetness and a honey-like flavor.

The analytical value of the fruit syrup purified using fresh activated carbon is 0 as shown in Table 1.

Acidity (C%) IN/l O Based on the titration number with sodium hydroxide, the corresponding ratio as anhydrous citric acid is shown.

NH2-N (~壬): The amount of amino nitrogen determined by the Vansteig method, expressed as the m9 number in a sample of 70θ.

Hesveridin (Cmg%): Measured by modified Davis method and expressed as the number of η in 100 g of sample.

Color tone (4"'rm/j,) indicates the absorbance value of light at a wavelength of 4"'mμ.

Ca (ppm): Data 100 by M absorption method
The amount of calcium in 0 is shown in m.〇Table 1 Flavonoid-free fruit juice obtained by using new activated carbon Next, an aqueous solution of enoic acid based on λ for the above used activated carbon, g39, ?
o OKg was added, and the mixture was placed in a steam-heated double pot and heated at 95 to 1ooc for 70 minutes while stirring, then P was separated using an Oliver filter, and recycled activated carbon (hydrated) goKy
Then, λλD kg of recovered citric acid water bath solution was obtained.

This recycled activated carbon goKy was mixed with secondary fruit juice 9009 obtained by liming and pressing the juice lees of Unshiyu mandarin oranges in the same manner as before, and heated to 40% at 90 to 100C as before.
After heating and stirring for a minute, the liquid was separated using an Oliver filter, and a clear syrup [corresponding to [flavonoid-free fruit juice (2)] in Table 2 shown below) was obtained along with activated carbon (water-containing) glKy.

Obtained 0 Ky. Concentrate this syrup in the same way as before and obtain Br1x20
'' thick syrup [Bx in Table 2, 7 o deflavonoid fruit juice (corresponding to February) 10!; Kf was obtained.

The appearance and flavor of this thick syrup were almost the same as the first thick syrup CBx, 7o-deflavonoid (1)). Table 2 shows the analytical values of the full sheet syrup using this recycled activated carbon.
g/Kf of recovered activated carbon.

In the same manner as in the regeneration method described above, 7 g of bioactive charcoal was mixed with double the amount of 12% citric acid water bath solution, stirred and kept at 100C for 10 minutes, and then filtered again using an Oliver filter.
Kg and recovered citric acid aqueous solution λjoKy were obtained.

This activated carbon glKy was mixed with 900 UP of secondary fruit juice in the same manner as before, heated and stirred at 90 to 100C for 40 minutes, P was separated using an Oliver filter, and recovered activated carbon glKy and transparent syrup [below "Deflavonoid fruit juice (corresponding to March") in Table 3
I got f. Next, this was concentrated to give a thick syrup of Br1x 7 oo [r Bx, 7 in Table 3].

Flavonoid-free fruit juice (equivalent to March) g/9
I got Kf. This is the first thick syrup (BX, 7
Table 3 shows the analytical values of the fruit syrup using this bioactive charcoal, which had almost the same appearance and flavor as 0-free flavonoid [1].

Table 3 Example of flavonoid-free fruit juice using recycled activated carbon 2 [Second fruit juice C fruit syrup made from squeezed summer mandarin juice lees]
Reuse of activated carbon when manufacturing] Natsumikan J
The lees obtained by squeezing 000 Kf with an in-line juicer,
namely, a mixture of exocarp, endocarp, sac, and seeds;
The so-called juice lees λ00 is made by mixing the fruit juice with the pulp that is separated using an innitsher and a centrifuge.
0 [/, add 10Ky of slaked lime, mix for about io minutes, press with a screw press and g! OKy secondary fruit juice and about 1ioocy of cake were obtained.

Put this secondary fruit juice into a steam-heated double pot and adjust the pH to 5 to 2.
Heat rapidly while adjusting to qi-io.

After stirring for 75 minutes as C, transfer it to another storage tank and leave it overnight. Next, transfer this supernatant liquid g00Kf to the previous double boiler. -/ Add 11.0 Ky of powdered activated carbon while heating to 00'C, stir while maintaining the above temperature for ≦0 minutes, separate with an Oliver filter, and use activated carbon (hydrated) / 1109 and fruit juice 7ooKy [
Corresponding to "flavonoid-free fruit juice (1)" shown in Table 4 below] was obtained. This fruit juice is concentrated under low temperature and reduced pressure to produce Br.
1x 70° thick syrup [r Bx in Table 4,
7 o Deflavonoid fruit juice (corresponding to 1) lo4
This syrup is a pale orange transparent viscous liquid with a mild sweetness and uniform flavor.

Table 4 shows the analytical values of the fruit syrup purified using fresh activated carbon as described above.

In addition, naringin was measured by Davis modified method, and sample 1
Table 4 Deflavonoid fruit juice obtained by using new activated carbon Next, put the above-mentioned used activated carbon (water-containing) itioKy into a steam-heated double boiler, and add 1000 Kp of 3-layer citric acid water bath. The mixture was mixed and heated at 93 to 100 C for 1S minutes while stirring, and then separated using an Oliver filter to obtain regenerated activated carbon (hydrated)/Jg9.

Using this recycled activated carbon/3 tEy, in place of the above-mentioned new activated carbon, it was added to 900M supernatant liquid obtained by heating and cooling the secondary fruit juice in the same manner, stirred at 93-10DC for 10 minutes, and filtered. Activated carbon (hydrated)/1IIKf and fruit juice [Deflavonoid-free fruit juice (2) in Table 5 below]
700 Kf was obtained.

This fruit juice was concentrated under low temperature and reduced pressure to obtain a concentrated syrup of Br1 x 70' [corresponding to rBx, 70 deflavonoid fruit juice (2) in Table 5] lλ3 Ey.

Table 5 shows the analytical values of the fruit syrup purified using Totogu's recycled activated carbon.

Table 5 Flavonoid-free fruit juice obtained by using recycled activated carbon Activated carbon recovered during purification using the above-mentioned recycled activated carbon (water-containing form) / 4 / [y = 3 citric acid water bath solution / 000
Kl was added, heated and stirred at 9J to 100C for 1S minutes, and filtered again to obtain living carbon (C hydrous) lllOKf, which was added to 900 tips of the supernatant obtained by heating and cooling beer water in the same manner as above. Plus, 9! ; Stir at -100C for 10 minutes, filter, and recover activated carbon (water-containing) i<togy
and fruit juice [[flavonoid-free fruit juice (in Table 6 shown below]
[corresponding to March] 7 units o Ey was obtained, and this was further condensed under reduced pressure to obtain a concentrated syrup of Br1x 70' [corresponding to rBx, 7θ deflavonoid fruit juice (3) in Table 6']
j20Kf was obtained.

Table 6 shows the analytical values of the fruit syrup purified using the bioactive charcoal as described above.

Table 6. Flavonoid-free fruit juice obtained by using biogenic charcoal As mentioned above, even when biogenic charcoal is used, the de-naringin effect is excellent.
Sensory comparisons showed that the fruit juice obtained was no different from the juice made using new activated carbon (and almost no bitterness was felt).

Example 3 [Reuse of activated carbon when producing whole fruit juice (compounded juice) from grapefruit] Grapefruit 1000Ky was crushed with a hammer crusher, 0θMy water was added thereto, and the mixture was polished using a high-speed rotating mill. After crushing, the average particle diameter is 100-130.
The fruit is pulverized down to microns, then instant heat sterilized for 9λ~93C130~aO seconds using a tube heater, and then rapidly cooled to produce a creamy viscous fruit juice.
Of the 0 obtained Lf, divide g009 and water<t o
o Pectin-degrading enzyme (pectinol) is added and dispersed in the fruit juice diluted with Ey, and
After reacting for a day and night in soC, diatomaceous earth was added as a filter aid and filtered through a filter press to obtain transparent grapefruit juice [hereinafter referred to as "clarified juice"].

Corresponds to “unprocessed fruit juice” in Table 7 below]t
, 5ocy was obtained. This is a slightly orange colored juice with a very bitter taste. Put this in a steam-heated double pot, add new powdered activated carbon/j, 4 Kf, and boil for SO~5s.
r): Heat and stir for x0 minutes, collect activated carbon [hydrated]'j79 with an Oliver filter, add diatomaceous earth to the fruit juice, filter it, and remove the [flavonoid-free fruit juice (equivalent to January) in Table 7]. ] Otsu l.

I got Ky. This was further concentrated under reduced pressure to obtain Br1x 7
Concentrated to 0.00, slightly orange transparent grapefruit concentrated fruit juice [rBx in Table 7, 7o deflavonoid fruit juice (1
)” 2 Eys were obtained.

Table 7 shows the analytical values of the above-mentioned Totogu fruit juice purified using new activated carbon.

Table 7 Grapefruit juice using new activated carbon Next, add 2-width citric acid water bath solution /109 to the recovered activated carbon (hydrated) l17Ky, heat and stir at 9S to 100C for /j minutes, filter with an Oliver filter, and regenerate. Activated carbon (hydrated) xi A 9 was obtained. This recycled activated carbon 4 (A Kf
was added to transparent 1 juice TGOYY in the same manner as purification using new activated carbon, and subjected to flavonoid removal treatment to obtain fruit juice [``Deflavonoid fruit juice (2)'' in Table 8 shown below]
]600Ky and activated carbon (hydrated) <l j
The mackerel was collected. The fruit juice is concentrated to Br1x 70° to obtain concentrated grapefruit juice [rBx in Table 8, 70
7 o Ky corresponding to "flavonoid-free fruit juice" was obtained.

Table 8 shows the analytical values of grapefruit juice purified using recycled activated carbon. Hydrous carbon) pscy was heat-treated in a citric acid water bath under the same conditions as the regeneration above to regenerate activated carbon (hydrocarbon) 4AKj.
I got 1L 0 This is the same as last time, clear grapefruit juice A! 21ff was added to roKy, and flavonoid removal treatment was performed to obtain fruit juice [corresponding to [flavonoid-free fruit juice (3) J] in Table 9 shown below) AOOKy, and at the same time, activated carbon [hydrated] 59 was collected. This fruit juice B
Concentrated grapefruit juice (corresponding to "BX, 70 flavonoid-free fruit juice" in No. 9) was obtained by concentrating to r1X70° to obtain 70Fy-.

Table 9 shows the analytical values of grapefruit juice purified using recycled activated carbon as described above. The flavonoid effect was strong, and compared to the juice made using fresh activated carbon, no sensory differences were observed, and almost no bitterness was felt.

Example 4 [Reuse of activated carbon when producing secondary fruit juice from squeezed fruit juice of summer mandarin oranges] In Example 2, instead of using citric acid to regenerate activated carbon, malic acid was used. A secondary fruit juice from the squeezed lees of summer mandarin oranges was purified under the same conditions as in Example 2. In other words, 900 q of secondary fruit juice was mixed with 27 q of fresh powdered activated carbon.
Purify in seconds to obtain purified fruit juice of g cores, and add malic acid water bath solution aOOKy to activated carbon (water-containing) g and jKy collected here, place in a steam-heated double boiler, and stir. After heating at 93 to 1 OoC for 10 minutes,
Passed through an Oliver filter, recycled activated carbon (hydrated) g
/Kf was obtained. Using this recycled activated carbon, it was added to 900 Ky of secondary fruit juice and heated at 90 to 100 °C to produce flavonoid fruit juice g/3Kf and recovered activated carbon (C hydrated) gOKy.
I got it. This recovered activated carbon is mixed with 211J malic acid aqueous solution.
Heat and stir for 70 minutes at 00 Kf and 90 to 1 OOC, filter once through an Oliver filter, and reconstitute living carbon (hydrated) g.
I got ocy. Using this re-living charcoal, it is qoo
It was added to the secondary fruit juice of Ky and heated and stirred at 9S to 100C for 'l/, θ minutes to obtain 3M of flavonoid-free fruit juice.

The analytical values of fruit juice purified using recycled activated carbon and recycled activated carbon are shown.

As can be seen in Table 10, the flavonoid removal effect of activated carbon is about 4 compared to using new activated carbon. However, at the concentration of straight fruit juice, fruit juice with such a high naringin content has almost no bitter taste sensually.

Example 5 [Reuse of activated carbon when producing secondary fruit juice from squeezed fruit juice of summer mandarin oranges] The same procedure as Example 2 was performed except that tartaric acid was used instead of citric acid for regenerating the activated carbon in Example 2. A secondary fruit juice from the squeezed lees of summer mandarin oranges was purified under the same conditions. That is, first, the secondary fruit juice lθ00M was mixed with fresh powdered activated carbon 3
Purified fruit juice was purified using 0-liquid to obtain 900 M of purified fruit juice, and the recovered activated carbon (water-containing) g3Ky was added with an aqueous tartaric acid solution, J009, and placed in a stainless steel double pot with a stirrer, and heated to 900 M while stirring. After heating at -100'Q for IO minutes, the mixture was filtered through an Oliver filter to obtain 3Ey of regenerated activated carbon (hydrated). Using this recycled activated carbon, add it to the secondary fruit juice 90'OEf and add 90S-100
The mixture was heated at C to obtain flavonoid-free fruit juice gλo Kg and 1 recovered activated carbon (hydrated) g21p. This recovered activated carbon,
The mixture was heated and stirred at 90~/DOC for 10 minutes in an aqueous solution of λ tartaric acid 300, and filtered through an Oliver filter to obtain living carbon (water-containing) gDKp. Using this reactivated charcoal, add it to 9 o o Ky of secondary fruit juice and make 95 to 1
Stir for 0 minutes at 0°C and heat.

Flavonoid-free fruit juice GL! Kf and recovered activated carbon (water-containing) KO mark were obtained.

Table 11 below shows the new activated carbon mentioned above.

The analytical values of fruit juice purified using recycled activated carbon and recycled activated carbon are shown.

As shown in Table 11, the effect of removing flavonoids is.

Compared to citric acid and malic acid, tartaric acid is the most superior, and the flavonoid-free fruit juice made using activated charcoal is almost sensually different from the fruit juice made using fresh activated charcoal (no bitterness is found). It was something I couldn't feel.

Applicant: Nankai Kako Co., Ltd.

Claims (1)

[Scope of Claims] (1) A method for purifying citrus fruit juice or juice obtained from its juice residue by treating it with activated carbon. Heating activated carbon to be reused with a water bath solution of citric acid, malic acid, or tartaric acid. A method for regenerating activated carbon for purifying citrus juice, characterized by
The regeneration method according to claim 1. (3) The regeneration method according to claim 1, wherein the concentration of the water bath solution of citric acid, malic acid, or tartaric acid is 0.3 to 1 Oqb.