JP5222124B2 - Production method of feed or fertilizer using fermentation residue - Google Patents

Description

  The present invention relates to a method for producing a feed or fertilizer using a fermentation residue, and in particular, to a method for producing a feed or fertilizer using a fermentation residue that can efficiently remove metal ions from the fermentation residue.

  In 1993, a number of countries, including Japan, adopted the London Convention (the Convention on the Prevention of Marine Pollution from Waste and Other Disposals). Although fermented distillation residue is currently recognized as an exempted item from the Convention, as a matter of fact, it is difficult to continue conventional ocean dumping as it is. Has been made.

  Fermentation distillation residues, such as shochu, usually contain water and solids, and the water contains 90% by weight or more, and the solids contain a large amount of protein, starch, fiber and the like.

  Although incineration is also conceivable as a land treatment of such fermentation distillation residue, it is not a preferable method because the burden of fuel costs as incineration equipment and a combustor increases.

  In recent years, there has been an increase in the use of fermented distillation residue as livestock feed, coupled with the impact of soaring feed prices.

  Shochu contains oxycarboxylic acids such as citric acid, amino acids such as glutamic acid, polyphenols, etc., and also contains crude protein components, so it is highly valuable as a raw material for livestock feed. However, if shochu is left for half a day or a day at an outside temperature, a rotting odor is generated and the taste of the livestock is reduced. Therefore, the shochu is concentrated.

  Shochu contains a relatively large amount of ingredients such as citric acid and acetic acid that prevent spoilage. Thus, by concentrating shochu containing only 5 to 10% of solid content and increasing the amount of crude protein, the concentration of citric acid, etc., feed value and antiseptic properties (antibacterial properties) can be improved.

Shochu of brown sugar shochu is easier to concentrate than other shochu such as rice bran, rice and wheat, but the shochu concentrate of brown sugar shochu contains a high concentration of potassium. If a feed with a high content is given to livestock such as cattle, the content of magnesium or calcium relative to potassium is lowered, which may cause physiological disorders. For this reason, when fermenting distillation residues, such as shochu, are concentrated and used as a feed, it is necessary to remove metal ions, such as potassium ion, in a concentrate.
JP-A-64-38193 JP 2002-362990 A

  The subject of this invention is providing the manufacturing method of the feed or fertilizer using the fermentation residue which can remove a metal ion efficiently from fermentation residues, such as shochu.

  Other problems of the present invention will become apparent from the following description.

  The above problems are solved by the following inventions.

(Claim 1)
A concentration step for concentrating the fermentation residue to produce a fermentation residue concentrate, and a metal ion removal for permeating and removing alkali metal ions from the fermentation residue concentrate side obtained in the concentration step through a cation exchange membrane A method for producing feed or fertilizer using a fermentation residue.

(Claim 2)
The said concentration process concentrates solid content in the said fermentation residue to 15% or more, The manufacturing method of the feed or fertilizer using the fermentation residue of Claim 1 characterized by the above-mentioned.

(Claim 3)
The metal ion removal step uses an ion dialysis tank having a monovalent ion-exchangeable diaphragm in the concentrate chamber, and allows the monovalent cation to permeate by circulating the fermentation residue concentrate in the concentrate chamber. The method for producing feed or fertilizer using the fermentation residue according to claim 1, wherein the fermentation residue is removed.

(Claim 4)
The method for producing feed or fertilizer using the fermentation residue according to claim 1, wherein the fermentation residue is shochu made from brown sugar or koji.

(Claim 5)
The said concentration process concentrates the said fermentation residue using a multi-effect can, The manufacturing method of the feed or fertilizer using the fermentation residue in any one of Claims 1-4 characterized by the above-mentioned.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the feed or fertilizer using the fermentation residue which can remove a metal ion efficiently from fermentation residues, such as shochu, can be provided.

  Embodiments of the present invention will be described below.

  FIG. 1 is a flow sheet showing an embodiment of the present invention. In the figure, 1 is a storage tank for storing a fermentation residue that is a liquid to be treated, and 10 is a stirrer.

  In the present invention, the fermentation residue includes a liquid substance containing a large amount of solid content remaining after distillation of the alcohol in the process of producing distilled liquor, for example, shochu shochu, barley shochu, rice shochu, brown sugar shochu Alternatively, shochu such as a mixture of these, and distilled spirits produced during whiskey fermentation are also included. Of these, brown sugar shochu using brown sugar with a high potassium (K) content or shochu shochu using koji as a raw material is preferred, and brown sugar shochu is particularly preferred in the present invention. The fermentation residue of the present invention may be a garbage methane fermentation residue. Here, the case where brown sugar shochu is used as a fermentation residue will be described.

  The brown sugar shochu stored in the storage tank 1 is then sent to the solid-liquid separation means 2 for solid-liquid separation. As the solid-liquid separation means 2, an MF membrane (microfiltration membrane), a screw press, a rotary press, a vacuum dehydrator, a filter press, or the like can be used. Among them, an MF membrane or a screw press is preferable.

  By the solid-liquid separation by the solid-liquid separation means 2, the brown sugar shochu is separated into the solid content side and the liquid content side, and the liquid content side is sent to the concentration means 3 and concentrated by the concentration means 3 to concentrate the brown sugar shochu. A liquid (fermentation residue concentrate) is produced (concentration step).

  The brown sugar shochu to be sent to the concentration means 3 is preferably screen-treated.

  As the concentrating means 3, an evaporator can be preferably used. As the evaporator, a multi-effect can, a spray evaporator and the like can be used. Among them, it is preferable to use a multi-effect can, and since the viscosity of the liquid increases as the concentration progresses, it is preferable to use, for example, a reduced-pressure forced circulation multi-effect concentrator made by Mitsui Engineering & Shipbuilding.

  In this concentration means 3, in order to increase the removal efficiency (current efficiency) of metal ions in the subsequent metal ion removal step, it is preferable to concentrate the solid content concentration (TS) in brown sugar shochu to 15% or more, more preferably. Is to concentrate to 30% or more. This concentration can reduce the amount of ion dialysis, and can also increase dialysis efficiency (current efficiency).

The brown sugar shochu concentrate concentrated by the concentration means 3 is sent to the metal ion removing device 4, and the metal ions removing device 4 removes metal ions, particularly potassium ions (K ⁺ ) in the concentrated solution. (Metal ion removal step).

  In this invention, the metal ion removal apparatus 4 permeate | transmits and removes the potassium ion which is a monovalent cation from the brown sugar shochu concentrate obtained by the concentration means 3 through a cation exchange membrane.

  FIG. 2 shows an example of such a metal ion removing device 4. This metal ion removing device 4 is an example using a general ion dialysis tank (electrodialysis tank), and an anode 41 and a cathode 42 are disposed opposite to each other on opposite wall surfaces of an ion dialysis tank 40 constituting a concentrate chamber, In the meantime, the flow path 43 through which the brown sugar shochu concentrate, which is the liquid to be treated, and the flow path 44 through which the potassium ion concentrate removed from the brown sugar shochu concentrate are alternately arranged. The cation exchange membrane 45 and the anion exchange membrane 46 are alternately arranged between the flow paths 43 and 44, respectively. For the anode 41 and the cathode 42, an expanded metal obtained by coating titanium or the like with platinum or the like can be used.

Here, the cation exchange membrane 45 is a diaphragm that selectively transmits monovalent cations. Therefore, when a predetermined voltage is applied between the anode 41 and the cathode 42, potassium ions (K ⁺ ) are transferred from the brown sugar shochu concentrate flowing through the flow path 43 through the cation exchange membrane 45 to the cathode 42 side. It permeates to the adjacent channel 44 side and is removed from the brown sugar shochu concentrate in the channel 43. At this time, the anions in the brown sugar shochu concentrate also permeate through the anion exchange membrane 46 to the channel 44 side adjacent to the anode 41 side. There is no particular problem as long as it is removed.

  Although not shown, the brown sugar shochu concentrate and the potassium ion concentrate are circulated through the channels 43 and 44 by pumps (not shown), respectively.

  FIG. 3 shows another example of the metal ion removing device 4. This metal ion removing device 4 is a case where only a cation exchange membrane 45 is used, and an anode 41 and a cathode 42 are arranged opposite to each other on opposite wall surfaces of the ion dialysis tank 40, and a brown sugar shochu, which is a liquid to be treated, is placed therebetween. A plurality of sets in which the flow path 43 of the cocoon concentrate and the flow path 44 of the concentrated potassium ion solution removed from the brown sugar shochu concentrate are arranged via the cation exchange membrane 45 therebetween are provided. It has been. Reference numeral 47 denotes a bipolar plate (bipolar partition plate).

  Also in this aspect, brown sugar shochu concentrate and potassium ion concentrate are circulated through the flow paths 43 and 44 by pumps (not shown), respectively, and in the process, the voltage applied between the anode 41 and the cathode 42 Potassium ions can be permeated and removed from the brown sugar shochu concentrate side in the channel 43 to the adjacent channel 44 through the cation exchange membrane 45.

  Although it is a generally known technique to permeate and remove cations from a liquid using a cation exchange membrane as described above, in the present invention, this cation exchange membrane is used to permeate and remove potassium ions. In doing so, it has a feature in that brown sugar shochu is concentrated as a pre-process to prepare a brown sugar shochu concentrate. By removing the metal ions after using brown sugar shochu as a concentrate, the removal rate of potassium ions is higher than the removal of metal ions from brown sugar shochu as it is. The current efficiency for removal increases.

  This is due to the following knowledge of the present inventors. In other words, in ion dialysis using a cation exchange membrane, protons permeate in the same manner as potassium and sodium, and the proton permeation rate (which also involves the transport number) is usually higher than that of alkali metal ions. Becomes more than an order of magnitude larger. In addition, shochu is a relatively strong acid, so that the amount of proton permeation increases and the current efficiency of alkali metal removal is greatly reduced. The pH of shochu is about 4 or less, which is mainly due to organic acids such as citric acid. Therefore, the pH does not drop much even in a concentrated liquid (the proton concentration does not increase). Therefore, the current efficiency with respect to alkali metal ion removal increases as the concentration of the liquid increases.

  The brown sugar shochu concentrate from which potassium ions have been removed in this way is used as a livestock blended feed.

  Above, brown sugar shochu was used as the fermentation residue, but in the case of other shochu and garbage methane fermentation residue as well, monovalent cations could be efficiently removed from the concentrate and obtained. The concentrated liquid can be used as a mixed feed or a fertilizer.

  Examples of the present invention will be described below, but the present invention is not limited to such examples.

  The metal ion removal apparatus shown in FIG. 4 was used as a test apparatus, and a potassium ion removal test from brown sugar shochu was performed.

  In FIG. 4, 400 is an electrolytic solution (concentrated liquid such as potassium ions), 401 is an ion dialysis tank for storing the electrolytic solution, 402 is an anode made of expanded metal in a cylindrical shape in which titanium is coated with platinum, and 403 is titanium. This is a rod-shaped cathode coated with platinum. Reference numeral 404 denotes a cation exchange membrane (effective length: 5 cm, inner diameter: about 3 mm) wound around the outer periphery of the anode 402, 405 denotes a lead wire electrically connected to the anode 402, and 406 denotes a lead wire electrically connected to the cathode 403. is there.

  Reference numeral 407 denotes a T-shaped tube that is liquid-tightly attached to the lower end of the anode 402 around which the cation exchange membrane 404 is wound. The lower end portion 407a of the T-shaped tube 407 is closed, and an inflow tube 408 that penetrates the side wall of the ion dialysis tank 401 and protrudes to the outside is connected to a branch portion 407b that branches sideways from the midway portion.

  Reference numeral 409 denotes a T-shaped tube that is liquid-tightly attached to the upper end of the anode 402 around which the cation exchange membrane 404 is wound. The upper end portion 409a of the T-shaped tube 409 is closed, and the lead wire 405 is inserted so as to penetrate the closed portion. An outflow pipe 410 that penetrates the side wall of the ion dialysis tank 401 and protrudes to the outside is connected to a branch part 409 b that branches from the middle part of the T-shaped pipe 409 to the side.

  Inside the anode 402 of this test apparatus, unconcentrated brown sugar shochu (solid content concentration TS = 4.5%) subjected to a screen treatment of 710 μm and brown sugar shochu concentrate (solid content concentration TS = 15%) Were circulated at a flow rate of about 5 mL / min, and a voltage of about 3 V was applied between the two electrodes to remove potassium ions by the cation exchange membrane 402. The tank temperature at this time was 19 degreeC.

  As a result, as shown in Table 1, the current efficiency when potassium ions were removed from unconcentrated brown sugar shochu was about 11%, whereas when concentrated to TS = 15%, about 38%. %, And the effect of improving potassium ion removal efficiency by concentration was confirmed.

Flow sheet showing an embodiment of the present invention The figure which shows an example of a metal ion removal apparatus The figure which shows another example of a metal ion removal apparatus The figure which shows the test apparatus of the metal ion removal apparatus used for the Example

Explanation of symbols

1: Storage tank 10: Stirrer 2: Solid-liquid separation device 3: Concentration device 4: Metal ion removal device 40: Ion dialysis tank 41: Anode 42: Cathode 43, 44: Channel 45: Cation exchange membrane 46: Anion Exchange membrane 47: Bipolar plate

Claims (5)

A concentration step for concentrating the fermentation residue to produce a fermentation residue concentrate, and a metal ion removal for permeating and removing alkali metal ions from the fermentation residue concentrate side obtained in the concentration step through a cation exchange membrane A method for producing feed or fertilizer using a fermentation residue.   The said concentration process concentrates solid content in the said fermentation residue to 15% or more, The manufacturing method of the feed or fertilizer using the fermentation residue of Claim 1 characterized by the above-mentioned.   The metal ion removal step uses an ion dialysis tank having a monovalent ion-exchangeable diaphragm in the concentrate chamber, and allows the monovalent cation to permeate by circulating the fermentation residue concentrate in the concentrate chamber. The method for producing feed or fertilizer using the fermentation residue according to claim 1, wherein the fermentation residue is removed.   The method for producing feed or fertilizer using the fermentation residue according to claim 1, wherein the fermentation residue is shochu made from brown sugar or koji.   The said concentration process concentrates the said fermentation residue using a multi-effect can, The manufacturing method of the feed or fertilizer using the fermentation residue in any one of Claims 1-4 characterized by the above-mentioned.

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