JP5858799B2 - Liquid food manufacturing method and liquid food manufacturing apparatus - Google Patents

Description

  The present invention relates to a liquid food production method and a liquid food production apparatus. More specifically, the present invention relates to a method for producing a liquid food with a reduced histamine content and an apparatus for producing a liquid food with a reduced histamine content.

  In the production of foods such as seasonings, there are many things that include a process called fermentation, and foods that are manufactured including a fermentation process are called fermented foods. For example, fermented foods are widely produced all over the world from those made from plants such as soybeans, wheat, rice, and corn to those made from animals such as seafood. These fermented foods are made by adding salt, sugar, water, etc., if necessary, to plant raw materials or animal raw materials and adding microorganisms necessary for fermentation, or depending on the microorganisms attached to the raw materials. Fermented for a period. In these fermented products, many cases have been reported in which histamine is produced by decarboxylation of histidine, which is a constituent amino acid of a raw material, by an enzyme produced by a microorganism or an enzyme derived from the raw material (for example, Non-Patent Document 1, 2). This histamine may cause allergic food poisoning (see, for example, Non-Patent Document 3).

  As a method for reducing the content of histamine in fermented foods, methods for suppressing the production of histamine in the production process have been proposed (for example, see Patent Documents 1 and 2). However, these are not methods for removing histamine contained in fermented foods.

  Moreover, although the removal method of histamine which uses bentonite etc. as an adsorbent is shown (for example, refer patent document 3), in this method, in addition to initial investment, such as a stirring tank and filtration equipment, the addition amount of histamine adsorbent Therefore, the running cost such as the adsorbent cost and the disposal cost is high, and it is not a method suitable for industrial production. Further, when cooling of the histamine-containing solution or pretreatment of the histamine adsorbent is necessary, the running cost is further increased.

JP 2004-313113 A JP 2008-212051 A JP2011-229455A

Tokyo Health and Safety Research Center Annual Report, No. 55, pp. 13-22, 2004 Tokyo Metropolitan Institute of Health Annual Report, No. 53, pp. 95-100, 2002 National Institute of Health, No. 127, pp. 31-38, 2009

  An object of the present invention is to provide a liquid food production method and a liquid food production apparatus capable of reducing the content of histamine contained in the liquid food with a simple configuration.

The present invention includes a strongly acidic cation exchange resin contact step in which histamine is adsorbed by bringing a liquid food containing histamine into contact with a strongly acidic cation exchange resin having SO ₃ ⁻ as an ion exchange group, and the strong acid cation. After the exchange resin contact step, the liquid acid production method includes a regeneration treatment step of bringing the strong acid cation exchange resin into contact with an alkaline solution at 60 ° C. or higher to regenerate .

  In the method for producing liquid food, the liquid food is preferably a liquid food containing 1% by weight or more of salt.

  In the method for producing liquid food, the liquid food is preferably a liquid food further containing an amino acid.

  Moreover, in the manufacturing method of the said liquid food, it is preferable that the said liquid food is the soy sauce which used the fish soy made from seafood, or cereals.

  In the method for producing a liquid food, the strongly acidic cation exchange resin is preferably a macroporous type.

Further, in the liquid food production method, the strongly acidic cation exchange resin has a specific surface area of 200 m ² / g or more and an average pore diameter of 6 to 30 nm in the analysis by a nitrogen adsorption method in a dry state. And the pore volume is preferably 0.8 cm ³ / g or more.

The present invention also provides a strongly acidic cation exchange resin contact means for adsorbing histamine by bringing a liquid food containing histamine into contact with a strongly acidic cation exchange resin having SO ₃ ⁻ as an ion exchange group . a reproduction processing means for reproducing processing a cation exchange resin is contacted with 60 ° C. or more alkaline solutions, is a manufacturing apparatus for liquids foods Ru comprising a.

  Moreover, in the said liquid food manufacturing apparatus, it is preferable that the said liquid food is a liquid food containing 1 weight% or more of salt.

  Moreover, in the said liquid food manufacturing apparatus, it is preferable that the said liquid food is a liquid food containing an amino acid further.

  Moreover, in the said liquid food manufacturing apparatus, it is preferable that the said liquid food is the soy sauce using the fish soy which uses fishery products as a raw material, or grains.

  In the liquid food manufacturing apparatus, the strongly acidic cation exchange resin is preferably a macroporous type.

Further, in the apparatus for producing liquid food, the strongly acidic cation exchange resin has a specific surface area of 200 m ² / g or more and an average pore diameter of 6 to 30 nm in an analysis by a nitrogen adsorption method in a dry state. And the pore volume is preferably 0.8 cm ³ / g or more.

  In the present invention, by bringing a liquid food containing histamine into contact with a strongly acidic cation exchange resin, the content of histamine contained in the liquid food can be reduced with a simple configuration.

It is a schematic block diagram which shows an example of the manufacturing apparatus of the liquid food which concerns on embodiment of this invention.

  Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.

  A schematic configuration of an example of a liquid food production apparatus according to an embodiment of the present invention is shown in FIG. 1, and the configuration will be described. The liquid food production apparatus 1 shown in FIG. 1 includes a column 10 filled with a strong acid cation exchange resin as a strong acid cation exchange resin contact means, and a treatment liquid storage tank 12. Moreover, the liquid food manufacturing apparatus 1 may include an alkaline storage tank 14 as a regeneration processing unit.

  As shown in FIG. 1, an inflow line 16 is connected to the supply port of the column 10. One end of the discharge line 18 is connected to the discharge port of the column 10, and the other end is connected to the supply port of the processing liquid storage tank 12. A switching valve 26 is provided in the middle of the discharge line 18, and one end of the discharge line 20 is connected to the switching valve 26. A switching valve 24 is provided in the middle of the inflow line 16, one end of the alkali inflow line 22 is connected to the switching valve 24, and the other end is connected to the discharge port of the alkaline storage tank 14. A heat exchanger 28 is installed in the middle of the alkali inflow line 22.

  An example of the operation of the liquid food manufacturing method and the liquid food manufacturing apparatus 1 according to the present embodiment will be described. First, the histamine-containing liquid food containing histamine is supplied to the column 10 through the inflow line 16, and the histamine-containing liquid food is brought into contact with the strongly acidic cation exchange resin packed in the column 10 so that histamine is adsorbed ( Strong acid cation exchange resin contact process). Histamine in the histamine-containing liquid food is adsorbed on the resin due to its affinity with the strong acid cation exchange resin. Therefore, the treatment liquid discharged from the column 10 is a liquid food from which histamine is removed or reduced. The liquid food is discharged through the discharge line 18 and stored in the processing liquid storage tank 12.

  In the present embodiment, after the strong acid cation exchange resin contact step, the strong acid cation exchange resin is contacted with an alkaline solution at 60 ° C. or more, and the strong acid cation exchange resin is regenerated and repeatedly used. preferable.

  After the strongly acidic cation exchange resin contact step, in this embodiment, a cleaning liquid such as water is supplied to the column 10 through the inflow line 16, and the strongly acidic cation exchange resin in the column 10 is cleaned (pre-cleaning step). . By this washing, the liquid food remaining in the strong acid cation exchange resin is eluted into the washing liquid. The cleaning liquid used for cleaning is discharged out of the system through the discharge line 18 through the switching valve 26 and the discharge line 20.

  After the pre-cleaning step, for example, an alkaline solution such as a 1N sodium hydroxide aqueous solution is heated from the alkali storage tank 14 to about 80 ° C. by the heat exchanger 28 and then passed through the alkali inflow line 22 and the switching valve 24. The strong acid cation exchange resin in the column 10 is regenerated by being brought into contact with the alkaline solution (regeneration process step). By this regeneration treatment, organic substances such as histamine and proteins adsorbed on the strongly acidic cation exchange resin are eluted, and the histamine removal performance is restored. The regenerated effluent containing the eluted organic substances such as histamine and protein is discharged out of the system from the discharge line 18 through the switching valve 26 and through the discharge line 20.

  In the present embodiment, after the regeneration treatment step, a cleaning liquid such as water is supplied to the column 10 through the inflow line 16, and the strongly acidic cation exchange resin in the column 10 is cleaned (post-cleaning step). By this washing, an alkaline solution or the like remaining in the strong acid cation exchange resin is eluted into the washing solution. The cleaning liquid used for cleaning is discharged out of the system through the discharge line 18 through the switching valve 26 and the discharge line 20.

  According to such a liquid food production method and liquid food production apparatus according to the present embodiment, a liquid food containing histamine is brought into contact with a strongly acidic cation exchange resin to be contained in the liquid food with a simple configuration. The histamine content can be reduced.

  The histamine-containing liquid food to be treated in the present embodiment is not particularly limited as long as it contains histamine, and examples thereof include fish sauce made from seafood, soy sauce using cereals, and brewed sake. Soy sauce is defined by the JAS method, such as those obtained by treating grains such as soybeans, wheat, and rice by steaming or other methods and culturing Koji fungi.

Usually, in the case of a high salt concentration liquid having a salt concentration of 1% by weight or more, for example, a large amount of cations such as Na ⁺ and K ⁺ are present, so that these cations are preferentially adsorbed on the ion exchange resin. Although ion exchange with weakly basic components such as histamine is unlikely to occur, according to the method for producing liquid food and the apparatus for producing liquid food according to the present embodiment, a liquid having a high salt concentration with a salt concentration of 1% by weight or more The content of histamine can also be reduced in foods. In general, the salt concentration of fish soy is 20% by weight to 30% by weight, and the content of histamine can be reduced even in such fish soy having a high salt concentration.

  In addition, according to the method for producing liquid food and the apparatus for producing liquid food according to the present embodiment, even in liquid food containing amino acids, particularly in liquid food having an amino acid concentration of 0.5% by weight or more and high amino acid concentration, The content of histamine can be reduced with little influence on the concentration of amino acids related to the taste of food.

  As the strong acid cation exchange resin used in the present embodiment, a general-purpose resin generally used for industrial use can be used. For example, a macroporous strong acid cation exchange resin, a gel strong acid A cationic cation exchange resin or the like can be used. Of these strongly acidic cation exchange resins, the macroporous strong acid cation exchange resin is preferable in that the amount of histamine adsorbed is large. Here, the macroporous strong acid cation exchange resin has a large number of large pores (macropores) in the resin matrix, and the average pore diameter of the dried resin by the nitrogen adsorption method is generally used. Is 2 nm or more. A gel-type strongly acidic cation exchange resin is a resin whose matrix within the matrix is almost uniform and has only fine pores (micropores). Generally, the pore diameter of dried resin by nitrogen adsorption method Cannot be measured.

Examples of the macroporous strong acid cation exchange resin include styrene-divinylbenzene-based (ion exchange group is SO ₃ ⁻ ) copolymer. Examples of commercially available macroporous strong acid cation exchange resins include Amberlite 200CT, FPX62, Dowex 88 (above, manufactured by Dow Chemical Co., Ltd.), Diaion PK216, HPK25 (above, manufactured by Mitsubishi Chemical Corporation), and Lebatit. S2568 (made by LANXESS) etc. are mentioned.

Examples of the gel type strongly acidic cation exchange resin include styrene-divinylbenzene-based (ion exchange group is SO ₃ ⁻ ) copolymer. Examples of the commercially available gel-type strongly acidic cation exchange resin include Amberlite IR120B (manufactured by Dow Chemical Co.), Diaion SK1B (manufactured by Mitsubishi Chemical Corporation), Levacit S1467 (manufactured by LANXESS), and the like.

Of these macroporous strongly acidic cation exchange resins, resins having a small pore diameter, a large specific surface area and a large pore volume are preferred in view of a large amount of histamine adsorption. For example, in analysis by nitrogen adsorption method in the dry state, a specific surface area of 200 meters ² / g or more, preferably 200m ² / g~1000m the range of ² / g, an average pore diameter in the range of 6～30Nm, and a pore volume of 0.8 cm ³ / g or more, the resin is suitable and preferably in the range of 0.8cm ³ /g~2.0cm ³ / g. An example of such a resin is the above-mentioned Amberlite FPX62.

The ion type using the strong acid cation exchange resin is not particularly limited, and examples thereof include Na ⁺ (sodium) type, K ⁺ (potassium) type, Ca ⁺ (calcium) type, and H ⁺ (hydrogen) type. It is done. In general, liquid foods contain salt, so a strongly acidic cation exchange resin is prepared and used in the same type as the cation contained in the solution to be treated, so that the ionic composition of the liquid food is not significantly changed. Can be processed.

  In the example of FIG. 1 described above, the liquid food is brought into contact with the strong acid cation exchange resin by the column system in which the liquid food is passed through the column 10 filled with the strong acid cation exchange resin. The present invention is not necessarily limited to this as long as the state in which the cation exchange resin is in contact with the cation exchange resin can be secured. As another form, for example, the liquid food may be brought into contact with the strong acid cation exchange resin by a batch method in which the strong acid cation exchange resin is added to the liquid food. In terms of production efficiency, workability, etc., the column method is preferable to the batch method.

In order to process by the column system, for example, in the range of SV (space velocity) 0.5 to 10 (h ⁻¹ ), a liquid food having a flow rate of 1 to 50 times per filling volume of the strongly acidic cation exchange resin. Is preferably passed through the column 10.

When the strongly acidic cation exchange resin packed in the column 14 is washed with a washing liquid such as water after the strongly acidic cation exchange resin contacting step, for example, SV (space velocity) 0.5 to 20 (h ^-1 ), a washing liquid having a flow rate of 2 to 20 times per packed volume of the strong acid cation exchange resin is passed through the column 14 to wash the strong acid cation exchange resin, and into the resin layer. It is preferable to elute the remaining liquid food.

  As the regenerant used for the regeneration treatment, an alkaline solution is preferably used. For strongly acidic cation exchange resins, an acidic solution is generally used as a regenerant, but in this application, the histamine removal performance is not sufficiently recovered by the acidic solution. This is presumably because the protein adsorbed on the strongly acidic cation exchange resin is hardly eluted in the acidic solution. The present inventors can elute proteins adsorbed on the strongly acidic cation exchange resin in the alkaline solution rather than the acidic solution, and sufficiently restore the histamine removal performance of the strongly acidic cation exchange resin. I found that I can do it. The temperature of the alkaline solution used as the regenerant is preferably 60 ° C or higher, more preferably in the range of 80 ° C to 90 ° C. If the temperature of the alkaline solution is less than 60 ° C., the histamine removal performance may not be sufficiently recovered. The higher the temperature of the regenerant, the higher the elution efficiency of the adsorbed substance. However, when the temperature is too high, deterioration of the strongly acidic cation exchange resin tends to progress and the usable period of the resin may be shortened.

  The concentration of the alkaline solution is preferably from 0.1 to 2.0 N, more preferably from 0.5 to 1.5 N. The higher the alkali concentration of the regenerant, the higher the elution efficiency of the adsorbed substance. However, if the alkali concentration is too high, the deterioration of the strongly acidic cation exchange resin tends to progress and the usable period of the resin may be shortened. is there.

  As the alkaline solution, an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used.

For example, the regeneration agent may be regenerated with a flow rate of 0.5 to 10 times per filling volume of the strongly acidic cation exchange resin within a range of SV (space velocity) 0.5 to 6 (h ⁻¹ ). It is preferable to pass the agent through the column 10 to regenerate the strongly acidic cation exchange resin and to elute substances adsorbed on the resin.

When the strongly acidic cation exchange resin packed in the column 10 after the regeneration treatment is washed with a washing liquid such as water, the strongly acidic cation exchange resin is in the range of, for example, SV (space velocity) 0.5 to 20 (h ⁻¹ ). 2 to 20 times the flow rate of the cation exchange resin packed volume is passed through the column 10 to wash the strongly acidic cation exchange resin, and the alkaline solution remaining in the resin layer is eluted. It is preferable to make it.

  The temperature of the cleaning liquid in the pre-cleaning step and the post-cleaning step may be in the range of 10 ° C. to 80 ° C., for example.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.

<Example 1>
To a glass column with jacket (inner diameter 22 mm × height 1,000 mm), strongly acidic cation exchange resin (manufactured by Dow Chemical Company, AMBERLITE FPX62, styrene-divinylbenzene system (SO ₃ ⁻ ), macroporous type, sodium type, 200 mL of a specific surface area of 300 m ² / g, an average pore diameter of 16 nm, and a pore volume of 1.0 cm ³ / g were filled. Next, a constant temperature water bath with a circulation function is connected to the column jacket to circulate 30 ° C. water, and the temperature in the column is made as constant as possible. Then, commercially available fish soy (salt concentration is 23 wt%) is added to 30 ° C. After warming, the liquid was passed through the column at a liquid passing speed of SV4. Up to 200 mL from the start of liquid flow was discarded as a thin material, and column outlet liquids that were passed through 200 mL to 1,400 mL were collected together. The histamine concentration of the collected fish soy was measured by the high performance liquid chromatography method under the following conditions. Moreover, the total nitrogen concentration which is an index of the amino acid content of the collected fish soy was measured under the following conditions.

(High-performance liquid chromatograph measurement conditions)
Analysis organization: Analyzed at Japan Food Analysis Center.

(Total nitrogen concentration measurement conditions)
According to Kjeldahl method.

(Measurement of specific surface area, average pore diameter, pore volume)
The specific surface area, average pore diameter, and pore volume of the strongly acidic cation exchange resin were measured by a nitrogen adsorption method after drying.

<Example 2>
To a glass column with jacket (inner diameter 22 mm × height 1,000 mm), strongly acidic cation exchange resin (manufactured by Dow Chemical Company, AMBERLITE 200CT, styrene-divinylbenzene system (SO ₃ ⁻ ), macroporous type, sodium type, 200 mL of a specific surface area of 50 m ² / g, an average pore diameter of 32 nm, and a pore volume of 0.35 cm ³ / g) were filled. Next, a constant temperature water tank with a circulation function is connected to the column jacket to circulate 30 ° C. water, and the temperature in the column is made as constant as possible. The column was passed through SV4. Up to 200 mL from the start of liquid flow was discarded as a thin material, and column outlet liquids that were passed through 200 mL to 1,400 mL were collected together. The histamine concentration and total nitrogen concentration of the collected fish sauce were measured in the same manner as in Example 1.

<Example 3>
Jacketed glass column (inner diameter 22 mm × height 1,000 mm), strong acid cation exchange resin (Dow Chemical, AMBERLITE IR120B, styrene-divinylbenzene system (SO ₃ ⁻ ), gel type, sodium type, cross-linked 200 mL of divinylbenzene concentration of the agent: 8% by weight) was filled. Next, a constant temperature water tank with a circulation function is connected to the column jacket to circulate 30 ° C. water, and the temperature in the column is made as constant as possible. The column was passed through SV4. Up to 200 mL from the start of liquid flow was discarded as a thin material, and column outlet liquids that were passed through 200 mL to 1,400 mL were collected together. The histamine concentration and total nitrogen concentration of the collected fish sauce were measured in the same manner as in Example 1.

<Comparative Example 1>
Synthetic adsorbent (manufactured by Dow Chemical Co., AMBERLITE FPX66, styrene-divinylbenzene system (no ion exchange group), macroporous type, specific surface area 900 m ² / into a glass column with jacket (inner diameter 22 mm × height 1,000 mm) g, average pore diameter 8 nm, pore volume 8.2 cm ³ / g) was filled in 200 mL. Next, a constant temperature water tank with a circulation function is connected to the column jacket to circulate 30 ° C. water, and the temperature in the column is made as constant as possible. The column was passed through SV4. Up to 200 mL from the start of liquid flow was discarded as a thin material, and column outlet liquids that were passed through 200 mL to 1,400 mL were collected together. The histamine concentration and total nitrogen concentration of the collected fish sauce were measured in the same manner as in Example 1.

<Comparative Example 2>
Jacketed glass column (internal diameter 22 mm × height 1,000mm), weakly acidic cation exchange resin (Dow Chemical Co., AMBERLITE IRC76, acrylic -), macroporous, hydrogen form ^- divinylbenzene (COO) Filled. Next, a constant temperature water tank with a circulation function is connected to the column jacket to circulate 30 ° C. water, and the temperature in the column is made as constant as possible. The column was passed through SV4. Up to 200 mL from the start of liquid flow was discarded as a thin material, and column outlet liquids that were passed through 200 mL to 1,400 mL were collected together. The histamine concentration and total nitrogen concentration of the collected fish sauce were measured in the same manner as in Example 1.

  Table 1 summarizes the measurement results of the histamine concentration and the total nitrogen concentration in the untreated fish sauce, Examples 1 to 3 and Comparative Examples 1 and 2.

As is clear from Table 1, in Examples 1 to 3 using a strongly acidic cation exchange resin, the histamine concentration in fish soy can be significantly reduced, and fish soy with a low histamine content can be obtained. It was. In particular, in Examples 1 and 2 using a macroporous type strongly acidic cation exchange resin, the reduction range of histamine is large, the macroporous type is large, the specific surface area and the pore volume are large, and the average pore diameter is large. Example 1 using a strongly acidic cation exchange resin having a small (specific surface area of 200 m ² / g or more, average pore diameter in the range of 6 to 30 nm, and pore volume of 0.8 cm ³ / g or more) The histamine concentration could be reduced below the detection limit (0.5 mg / 100 g). Although the specific surface area and pore volume were large and the average pore diameter was small, in Comparative Example 1 using a synthetic adsorbent having no ion exchange group, the histamine concentration in fish sauce could not be reduced. In Comparative Example 2 using a weakly acidic cation exchange resin, although the histamine concentration was reduced, the reduction range was small, and it was not practically usable. Thus, in Examples 1-3 using a strongly acidic cation exchange resin, the content of histamine can be reduced in fish sauce, which is a high salt concentration liquid food with a salinity concentration of 1% by weight or more. It was.

  In all of Examples 1 to 3 and Comparative Examples 1 and 2, the value of total nitrogen, which is an index of amino acid content, before and after the treatment is almost unchanged, and the adsorption of amino acids on the adsorbent affects the product. There was no level. Thus, in Examples 1 to 3 using a strongly acidic cation exchange resin, the content of histamine could be reduced without substantially affecting the content of amino acids related to the taste of liquid food. .

  Next, regeneration experiment of the strong acid cation exchange resin was conducted.

<Example 4>
(First cycle)
A glass column with a jacket (inner diameter 22 mm × height 1,000 mm), strong acid cation exchange resin (manufactured by Dow Chemical Company, AMBERLITE FPX62, styrene-divinylbenzene system (SO ₃ ⁻ ), macroporous type, specific surface area 300 m ² / g, average pore diameter 16 nm, pore volume 1.0 cm ³ / g) was filled in 200 mL. Next, the commercially available fish soy was passed through the column. The temperature at the time of liquid flow was 30 ° C., and the liquid flow rate was SV4. From the start of liquid flow to 200 mL, it was discarded as a thin material, and the column outlet liquid that had passed through 200 mL to 1,400 mL was collected in a lump (first cycle). . The histamine concentration of the collected fish soy was measured in the same manner as in Example 1 by high performance liquid chromatography.

(2nd cycle)
The strongly acidic cation exchange resin after the first cycle was regenerated by the following method. Ion exchanged water as a washing liquid was passed through 2,000 mL at a liquid passing temperature of 30 ° C. and a liquid passing speed SV4 to wash fish soy remaining in the column. After pre-washing, 400 mL of a 1N aqueous sodium hydroxide solution at 30 ° C. was passed as a regenerant at a rate of SV4. After the regeneration treatment, 2,000 mL of ion-exchanged water as a cleaning liquid was passed at a liquid passing temperature of 30 ° C. and a liquid passing speed of SV8 to wash sodium hydroxide remaining in the column.

  After the post-washing, the commercially available fish soy was passed under the same conditions as in the first cycle, and the column outlet liquids that were passed from 200 mL to 1,400 mL were collected together (second cycle).

(3rd cycle)
The strongly acidic cation exchange resin after the second cycle was regenerated by the following method. Ion-exchanged water as a cleaning liquid was passed through 2,000 mL at a liquid passing temperature of room temperature (about 30 ° C.) and a liquid passing speed SV8 to wash fish soy remaining in the column (pre-washing step). After pre-cleaning, connect a constant temperature water tank with a circulation function to the column jacket to circulate 80 ° C. water, make the temperature inside the column as constant as possible, and then add 400 mL of 1N aqueous sodium hydroxide solution at 80 ° C. as a regenerant. The solution was passed through the column at a flow rate of SV4 (regeneration process step). After the regeneration treatment, 2,000 mL of ion-exchanged water as a cleaning liquid was passed at room temperature (about 30 ° C.) at a liquid passing speed of SV8 to wash sodium hydroxide remaining in the column (post-washing). Process).

  After the post-cleaning, the temperature of the thermostatic water tank with a circulation function is set to 30 ° C., the temperature in the column is set to 30 ° C., and the commercially available fish soy is passed under the same conditions as in the first cycle. The column outlet liquids that were passed through were collected together (third cycle).

(4th cycle)
The strongly acidic cation exchange resin after the third cycle was regenerated by the following method. Ion exchanged water as a washing liquid was passed through 2,000 mL at a liquid passing temperature of 30 ° C. and a liquid passing speed SV4 to wash fish soy remaining in the column. After pre-washing, 400 mL of a 1N aqueous hydrochloric acid solution at 30 ° C. was passed as a regenerant at a rate of SV4. After the regeneration treatment, ion-exchanged water as a washing liquid was passed through 800 mL at a liquid passing temperature of 30 ° C. and a liquid passing speed SV6 to wash hydrochloric acid remaining in the column. Next, 400 mL of a 1N aqueous sodium hydroxide solution was passed at a liquid passing temperature of 30 ° C. and a liquid passing speed SV4. Further, 1,400 mL of ion-exchanged water was used as a cleaning liquid, and the liquid passing temperature was 30 ° C. and the liquid passing speed. Water was passed through SV8 to wash sodium hydroxide remaining in the column.

  Next, the commercially available fish soy was passed under the same conditions as in the first cycle, and the column outlet liquids that were passed from 200 mL to 2,000 mL were collected together (fourth cycle).

  Table 2 summarizes the measurement results of the histamine concentration in the first to fourth cycle treatment solutions.

  As is apparent from Table 2, in the third cycle, the histamine removal performance of the strongly acidic cation exchange resin has sufficiently recovered in the flow through after regeneration using an aqueous sodium hydroxide solution heated to 60 ° C. or higher. It was. When a sodium hydroxide aqueous solution of less than 60 ° C. (30 ° C.) in the second cycle is used and hydrochloric acid and sodium hydroxide in the fourth cycle are used, the histamine in the treatment liquid is passed through after the regeneration. Concentration was high and histamine removal performance was hardly recovered.

  DESCRIPTION OF SYMBOLS 1 Liquid food manufacturing apparatus, 10 columns, 12 process liquid storage tank, 14 alkali storage tank, 16 inflow line, 18, 20 discharge line, 22 alkali inflow line, 24,26 switching valve, 28 heat exchanger.

Claims (12)

A strongly acidic cation exchange resin contact step in which a liquid food containing histamine is contacted with a strongly acidic cation exchange resin having SO ₃ ⁻ as an ion exchange group to adsorb histamine ;
After the strong acid cation exchange resin contact step, a regeneration treatment step of bringing the strong acid cation exchange resin into contact with an alkaline solution at 60 ° C. or higher for regeneration treatment;
A method for producing a liquid food, comprising: It is a manufacturing method of the liquid food according to claim 1,
The method for producing a liquid food, wherein the liquid food is a liquid food containing 1% by weight or more of salt. It is a manufacturing method of the liquid food according to claim 1 or 2,
The method for producing a liquid food, wherein the liquid food is a liquid food further containing an amino acid. It is a manufacturing method of liquid food given in any 1 paragraph of Claims 1-3,
A method for producing a liquid food, wherein the liquid food is fish soy made from seafood or soy sauce using cereals. It is a manufacturing method of liquid food given in any 1 paragraph of Claims 1-4,
The method for producing a liquid food, wherein the strongly acidic cation exchange resin is a macroporous type. It is a manufacturing method of the liquid food according to claim 5,
When the strongly acidic cation exchange resin is analyzed by a nitrogen adsorption method in a dry state, the specific surface area is 200 m ² / g or more, the average pore diameter is in the range of 6 to 30 nm, and the pore volume is 0.8 cm ^3. / G or more, The manufacturing method of the liquid food characterized by the above-mentioned. A strongly acidic cation exchange resin contact means for adsorbing histamine by bringing a liquid food containing histamine into contact with a strongly acidic cation exchange resin having SO ₃ ⁻ as an ion exchange group ;
A regeneration treatment means for regenerating the strongly acidic cation exchange resin by bringing it into contact with an alkaline solution at 60 ° C. or higher;
An apparatus for producing liquid food, comprising: An apparatus for producing a liquid food according to claim 7 ,
The apparatus for producing liquid food, wherein the liquid food is liquid food containing 1% by weight or more of salt. It is a manufacturing apparatus of the liquid food according to claim 7 or 8 ,
The apparatus for producing a liquid food, wherein the liquid food is a liquid food further containing an amino acid. It is a manufacturing apparatus of the liquid food according to any one of claims 7 to 9 ,
The apparatus for producing liquid food, wherein the liquid food is fish soy made from seafood or soy sauce using cereals. The manufacturing apparatus of the liquid food according to any one of claims 7-10,
The apparatus for producing liquid food, wherein the strongly acidic cation exchange resin is of a macroporous type. It is a manufacturing apparatus of the liquid food according to claim 11 ,
When the strongly acidic cation exchange resin is analyzed by a nitrogen adsorption method in a dry state, the specific surface area is 200 m ² / g or more, the average pore diameter is in the range of 6 to 30 nm, and the pore volume is 0.8 cm ^3. / G or more, The liquid food manufacturing apparatus characterized by the above-mentioned.

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