JP2001025763A - Treatment by beer lees and its treated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a removing method of the metal and the dye/dyestuff in waste water, which is economical, inexpensive, industrially easy in handling and convenient and to provide a beer lees or its treated material useful as a fertilizer/feeding stuff to which a metal ion is adsorbed. SOLUTION: A soln. such as waste water containing a metal compd. and the dye/dyestuff is brought into contact with the beer lees (including sparkling liquor lees) being the pressed residue of wort or its treated material to adsorb the metal ion and the dye/dyestuff to the beer lees or its treated material. As the beer lees treated material, the beer lees treated so that protein content may be >=40% and the beer lees treated material crossslinked with a crossslinking agent are exemplified.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a metal compound and / or a metal compound.
Or a method for removing and recovering metal ions and / or dyes / pigments dissolved in the solution from a solution such as wastewater containing dyes / pigments in a low-cost and simple manner, or filled with beer cake or a processed product thereof used for the method. The present invention relates to a filter, a beer lees to which metal ions are adsorbed, or a processed product thereof.

[0002]

2. Description of the Related Art Mineral and industrial wastewater contains various metals such as iron, copper and chromium. Since the metals contained in these wastewaters accumulate in the human body through fish and shellfish consumed by humans and cause serious adverse effects, a method for efficiently and inexpensively removing the metals contained in these wastewaters Is required. Conventionally, as a method for removing metals contained in wastewater, a neutralization method is generally used, and a method for removing metal ions as hydroxide precipitates has been adopted. However, metal hydroxides are difficult to coagulate and precipitate, so a great deal of time and effort is required for recovery, and because of the high water content of sludge, a large amount of waste is generated. Had become. Although a removal method using activated carbon, an ion-exchange resin, or the like has been proposed, restrictions are large due to economical problems or problems with the secondary treatment method.

[0003] Dyes and pigments contained in the wastewater not only increase the wastewater load, but also color the wastewater and cause river pollution. There is also a demand for a method for efficiently and inexpensively removing pigments. But these dyes
It is difficult to remove the pigment sufficiently by the general treatment method of wastewater such as the coagulation sedimentation method and the activated sludge method.
Conventionally, as a method for removing dyes and pigments contained in wastewater, a decolorization method using activated carbon and a method for decolorization using a cationic polymer flocculant have been proposed. However, there is a problem that the cost is high due to the necessity of the activated carbon, the replacement and activation of the activated carbon are complicated, and the selection of the flocculant is complicated and the cost is high even in the method using the polymer flocculant.

[0004] In recent years, as alternatives to these conventional treatment methods, methods of removing metals using biofilms such as algae and yeasts, proteins of animal origin, and peaches, and various treatment methods of various dyes and pigments have been proposed. ing. For example, JP-A-49-
No. 43875 discloses aluminum dissolved in a cation or non-dissociated form in an aqueous solution and an atomic number of 24.
A method is described in which a metal compound is brought into contact with a permanent tissue cell of a seed plant and the metal compound is adsorbed to the cell to remove and recover the metal compound from an aqueous solution.

Japanese Patent Application Laid-Open No. 56-113343 discloses that an aqueous medium containing a dissolved metal is at least one kind selected from the group consisting of feathers, wool, hooves powder, and one powder. The protein material includes the metal removed from the treated aqueous medium produced by contacting the dissolved metal with the dissolved metal for a time sufficient to convert the metal taken up by the protein material into a water-insoluble form. A method for recovering metals from the aqueous medium for separating loaded proteinaceous materials is described.

Japanese Patent Application Laid-Open No. 57-204283 discloses that wastewater containing iron, zinc and other heavy metal ions is brought into contact with raw peach or carbonized peach to remove iron ions by adsorption filtration, and then removes the iron ions from the wastewater. It describes a method for treating mine wastewater in which residual iron, zinc and other heavy metal ions are sulfurized with a sulfurizing agent, and then contacted with raw or carbonized fir and removed by adsorption filtration.

Japanese Unexamined Patent Publication (Kokai) No. 63-194793 discloses that various pollutants, such as various organic and inorganic substances, eutrophic substances, and coloring substances, contained in water are removed from plant seed coats such as rice husk charcoal. A method for removing pollutants in water adsorbed by a filter agent consisting of smoked or carbonized distillate is described.

In Japanese Patent Application Laid-Open No. 5-123885, hydrogen peroxide or titanium dioxide powder is added to waste water containing an organic dye, and ultraviolet light is irradiated to the waste water.
An organic dye-containing wastewater treatment method for generating H radicals and decomposing the organic dye, and a wastewater containing an organic dye containing divalent iron ions or monovalent copper ions together with hydrogen peroxide. A method of treating a wastewater containing an organic dye is disclosed, in which a compound is added and ultraviolet rays are irradiated to generate OH radicals to decompose the organic dye.

Japanese Patent Application Laid-Open No. 6-218378 discloses that an aqueous solution containing a reactive dye is made alkaline by adding an alkaline inorganic metal salt to pH 9 or higher, then by adding an inorganic acid to make it acidic to pH 6 or lower. A method for treating a waste residue containing a reactive dye for removing a substance that has changed insoluble in the treatment solution is described.

[0010] Further, Japanese Patent Application Laid-Open No. 9-141003 discloses that living organisms such as eggshell membranes, feathers and wool are used as raw materials.
Use a liquid adsorbent obtained by dissolving any of them in an alkaline solution such as a sodium hydroxide solution and then neutralizing with an acid, or a powdery adsorbent obtained by adding an acid to make it acidic. A metal occlusion method is described.

[0011] In addition, there is known a technique relating to a method for producing fertilizer using waste cake. For example, JP-A-10-21
No. 2187 discloses a process of adding at least one of activated sludge obtained by treating wastewater generated in a process of dyeing fibers or a process of producing food by an activated sludge method, rice bran, bran, sawdust and sake lees. , Streptomyces, microbis, actinomycetes belonging to Thermomonospora, Aspergillus, Rhizopus, Mucor, inoculated with at least one inoculum selected from the group consisting of filamentous fungi belonging to Penicillium, A method for producing an organic fertilizer comprising a step of stirring and fermenting is described.

Japanese Patent Application Laid-Open No. Hei 10-229826 discloses a low-calorie coal powder such as peat or peat added to a dry mixture of waste cake and caffeine-containing plant powder at the time of production of alcoholic beverages. Further, a method for producing a feed additive obtained by mixing ferrous sulfate and a carbonate of an alkali metal or an alkaline earth metal is described.

[0013]

Among the above-mentioned known wastewater treatment techniques containing metal compounds and / or dyes / pigments, JP-A-56-113343 and JP-A-57-20428.
No. 3, JP-A-63-194793, JP-A-Hei 9
JP-A-141003 can be evaluated in terms of effective use of waste.
As described in JP-A-003-003, a complicated pretreatment of dissolving a raw material in an alkali solution and then neutralizing with an acid is required, or as described in JP-A-57-204283.
Various post-treatment methods, such as post-treatment of heavy metal ions being sulfurized with a sulfurizing agent and then contacting with raw or carbonized fir, are sufficient from the viewpoints of practicality and economy. It was not a satisfactory way to get it.

An object of the present invention is to provide a simple method for removing metals and / or dyes and pigments in wastewater which is economically inexpensive and easy to handle industrially, and adsorb metal ions useful as fertilizers and feeds. An object of the present invention is to provide beer lees or a processed product thereof.

[0015]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and have produced beer lees, which are by-products produced in large quantities, inexpensive and easy to handle, or processed products thereof. In addition, they have found that they have excellent metal adsorption ability and excellent dye / dye adsorption ability, and have completed the present invention.

That is, according to the present invention, a solution such as waste water containing a metal compound and / or a dye / dye is brought into contact with beer lees or a processed product thereof, and the metal ions and / or dye / dye in the solution are converted into beer lees or beer lees. A method for treating a metal compound and / or a dye / colorant-containing solution with beer cake or a treated product thereof, wherein the protein content is 40% or more as a processed beer cake. The present invention relates to the above-mentioned treatment method using the processed beer cake processed material and the above-mentioned processing method using a beer cake processed product cross-linked by a crosslinking agent as the processed beer cake product.

The present invention also relates to a beer grain or a processed product thereof, wherein metal ion is adsorbed, wherein a solution containing a metal compound is brought into contact with beer cake or a processed product thereof.
The processed beer lees or the processed beer lees adsorbing the metal ions, which is the processed beer lees processed so that the protein content is 40% or more, the processed beer lees are cross-linked by a crosslinking agent. The present invention also relates to a beer lees processed product obtained by adsorbing the above metal ions, which is a processed beer lees product.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Beer lees used in the present invention is obtained by saccharifying malt obtained by germinating barley, followed by filtration.
Refers to the residue excluding wort, may be anything that is by-produced during normal beer production, and is not limited by the type of barley, the presence / absence of auxiliary materials, etc., In addition, the residue excluding wort similarly produced in the production of so-called low-malt beer in which the usage ratio of malt is reduced (hereinafter referred to as “low-malt beer lees”) is also included in the beer lees of the present invention. And the beer lees and sparkling sake lees of the present invention or their processed products are insoluble components in water in the residue after squeezing wort, for example, barley husk and insoluble proteins, and insoluble substances derived from hops and the like. It is included.

The processed beer cake in the present invention specifically includes a high protein content beer meal having a protein content of 40% or more and a high fiber content beer meal. These high protein content beer lees having a protein content of 40% or more and high fiber content beer lees can be obtained, for example, by the method described in Japanese Patent Publication No. 4-31666. In this method, beer cake in a wet state is pressure-pulverized by a roll mill having a roll gap of 0.1 to 0.3 mm, and the pressed powder is supplied to a vibrating sieve in the presence of water to be sieved. In the method, the processed beer cake having a protein content of 40% or more is treated as a fraction having a sieve mesh size of 20 to 50 mesh (hereinafter referred to as "MPF fraction") and a beer lees treatment containing a large amount of fiber. The product is obtained as a remaining fraction (hereinafter referred to as "husk fraction") on a sieve having a sieve mesh size of 5 to 20 mesh.

Further, the treated beer cake of the present invention is obtained by crosslinking beer cake or the above-mentioned treated beer cake with a trifunctional crosslinking agent such as triacryloylhexahydro-1,3,5-s-triazine. Crosslinked beer lees and crosslinked MP
F. As the crosslinking method, a usual crosslinking method can be used. For example, the above-mentioned crosslinked beer lees can be prepared by adding 5-200 parts by weight of a crosslinking agent to 100 parts by weight of beer lees and heating.

The solution containing the metal compound and / or the dye / pigment in the present invention can be specifically exemplified by industrial wastewater.
Any solution containing a dye may be used,
For example, it may be an aqueous solution of a metal compound or a pigment prepared at a predetermined concentration, which is used in the case of producing a fertilizer, feed, feed, or the like described later. Examples of the metal constituting the metal compound include iron, mercury, copper, nickel, cobalt, and chromium. Examples of the dye / pigment include anionic dyes (CIAcid Orange 7, CIAcid Re
d 88) and a dye having a metal element in the molecule (eg, copper phthalocyanine dye).

The treatment of the metal compound and / or the dye / pigment-containing solution with the beer lees or the processed product thereof of the present invention includes, for example, the water-insoluble beer lees or the processed product thereof used in the present invention. And / or 0.01 to 1 with respect to 100 parts of a solution such as waste water containing a dye or a pigment.
0 parts, and the mixture is stirred at 10 to 80 ° C. for 0.5 to 100 hours to adsorb metal ions and / or dyes / dyes on the beer lees or the processed product thereof, and then these beer lees or the processed product thereof The metal ions and / or dyes / pigments can be easily removed simply by subjecting to a solid-liquid separation from the solution.
In addition, by using a filter filled with beer lees or a processed product thereof, the solution to be treated is caused to flow down and, if necessary, circulated down the packed bed in the filter, so that metal ions and / or dye / The dye can be easily removed. In addition, metals, dyes, and pigments can be collected as necessary from beer grains adsorbed with metal ions and / or dyes or pigments or processed products thereof.

The beer meal adsorbed with metal ions of the present invention or a processed product thereof can be obtained by contacting a solution containing a metal compound with beer meal or a processed product thereof. Beer lees or a processed product thereof adsorbing such metal ions,
It can be expected to be used as a fertilizer, feed / feed, and food material. And, in the case of fertilizer applications, wastewater can be used as a solution containing a metal compound, and when beer lees or a processed product thereof to which metal ions in wastewater are adsorbed is used as a fertilizer raw material, beer lees or a processed product thereof can be used. The adsorbed metal ions do not easily flow out due to rainwater or the like, and are used as effective mineral components such as microorganisms for a long period of time.

In the case of use as a feed, feed or food material, a solution containing a metal compound as a mineral source useful for livestock, fish and shellfish, and humans is adjusted to a predetermined concentration in advance, and this solution is added to beer cake or beer lees. It is preferable to contact the treated material. Examples of the metal compound useful as a mineral source useful for livestock, seafood, and humans include zinc salts such as zinc gluconate and zinc sulfate, iron salts such as ferric chloride, and copper salts such as copper sulfate. . In addition, using a feed that adsorbs a red dye or the like to beer lees or a processed product thereof,
It can also be expected to improve the color of ornamental birds and fish.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the technical scope of the present invention is not limited to the following examples. In the following examples, an inductively coupled plasma emission spectrometer manufactured by Seiko Denshi Kogyo KK was used to measure the metal ion concentration, and an ultraviolet / visible spectrophotometer (manufactured by Hitachi, Ltd.) was used to measure the amount of dye adsorbed. "11
00 type)).

Example 1 Dried beer cake, dried MPF fraction as a processed beer cake,
And the dry barley hull fraction as a control was 0.0% each
5 g each was placed in a test tube with a stopper and the FeCl ₃ solution was added to a pH 4 solution.
Diluted with 0.1 M acetate buffer of
50 ml of a metal solution containing 20 ppm was added. After shaking the test tube at 30 ° C. for 24 hours, it was centrifuged, the metal ion concentration of the supernatant was measured, and the adsorption rate (%) was calculated. The results are shown in (Table 1).

[0027]

[Table 1]

Example 2 Dried beer lees, dried MPF fraction as processed beer lees,
And the dry barley hull fraction as a control was 0.0% each
5 g of each solution was placed in a stoppered test tube, and the HgCl ₂ solution was added to a pH 6 solution.
Diluted with 0.1 M-acetate buffer solution of
50 ml of a metal solution containing ２０20 ppm was added. After shaking the test tube at 30 ° C. for 48 hours, the tube was centrifuged, the metal ion concentration of the supernatant was measured, and the adsorption rate (%) was calculated. The results are shown in (Table 2).

[0029]

[Table 2]

Example 3 Dried beer lees, dried MPF fraction as processed beer lees,
And the dry barley hull fraction as a control was 0.0% each
5 g each was placed in a test tube with a stopper and the CuCl ₂ solution was added to a pH 6 solution.
Diluted with 0.1 M acetate buffer of
50 ml of a metal solution containing 20 ppm was added. After shaking the test tube at 30 ° C. for 48 hours, the tube was centrifuged, the metal ion concentration of the supernatant was measured, and the adsorption rate (%) was calculated. The results are shown in (Table 3).

[0031]

[Table 3]

Example 4 A dried beer lees, a dried MPF fraction as a processed beer lees and a dried barley hull fraction as a control were each 0.05%.
g of the K ₂ Cr ₂ O ₇ solution at pH6.
Was diluted with 0.1 M acetate buffer, and 50 ml of a metal solution containing 2 to 20 ppm as chromium ions was added. After shaking the test tube at 30 ° C. for 48 hours, the tube was centrifuged, the metal ion concentration of the supernatant was measured, and the adsorption rate (%) was calculated.
The results are shown in (Table 4).

[0033]

[Table 4]

Example 5 A dried beer lees, a dried MPF fraction as a processed beer lees and a dried barley hull fraction as a control were each 0.05%.
Each g of the solution was placed in a test tube with a stopper, and the NiCl ₂ solution was diluted with a 0.1 M acetate buffer solution at pH 6, and 50 ml of a metal solution containing 2 to 20 ppm as nickel ions was added. After shaking the test tube at 30 ° C. for 48 hours, the tube was centrifuged, the metal ion concentration of the supernatant was measured, and the adsorption rate (%) was calculated.
The results are shown in (Table 5).

[0035]

[Table 5]

Example 6 A dried beer lees, a dried MPF fraction as a processed beer lees and a dried barley hull fraction as a control were each 0.05%.
Each g of the solution was placed in a test tube with a stopper, and the CoCl ₂ solution was diluted with a 0.1 M acetate buffer solution of pH 6, and 50 ml of a metal solution containing 2 to 20 ppm as cobalt ions was added. After shaking the test tube at 30 ° C. for 48 hours, the tube was centrifuged, the metal ion concentration of the supernatant was measured, and the adsorption rate (%) was calculated.
The results are shown in (Table 6).

[0037]

[Table 6]

Example 7 As a processed beer cake, 0.05 g of the dried MPF fraction and 0.05 g of the dried barley hull fraction as a control were each placed in a test tube with a stopper, and the Pb (NO ₃ ) ₂ solution was adjusted to pH 6. 0.1M-
After dilution with an acetate buffer, 50 ml of a metal solution containing 2 to 20 ppm as lead ions was added. Keep this test tube at 30 ° C
After shaking for 48 hours, the mixture was centrifuged, the metal ion concentration of the supernatant was measured, and the adsorption rate (%) was calculated. The results (Table 7)
Shown in

[0039]

[Table 7]

Example 8 As a processed beer cake, 0.05 g of a dry barley husk fraction as a control of a dry MPF fraction was placed in a test tube with a stopper each, and the Cd (NO ₃ ) ₂ solution was adjusted to pH 6 Diluted with 0.1 M-acetate buffer, 2 to 20 pp as cadmium ion
50 ml of a metal solution containing m. This test tube is 3
After shaking at 0 ° C. for 48 hours, the mixture was centrifuged, the metal ion concentration of the supernatant was measured, and the adsorption rate (%) was calculated. The results are shown in (Table 8).

[0041]

[Table 8]

Example 9 Dry MPF fraction and dry MPF
5.0 g of the fraction and 0.004 mol of triacryloylhexahydro-1,3,5-s-triazine (manufactured by Daito Chemical Co., Ltd.) were added to a pH 11 sodium carbonate buffer [0.1 M- (NaHCO ₃ + Na ₂ CO _{3)]. 3} )] 200m
l, suspended at 80 ° C for 90 minutes, filtered, washed sufficiently with acetone, and dried and pulverized to obtain a crosslinked MPF-1. As a control, a dried barley husk fraction and crosslinked husk-1 obtained by subjecting the dried barley husk fraction to a cross-linking treatment in the same manner as above were used. Dry MPF fraction, crosslinked MPF-1, dried barley husk fraction, crosslinked husk-1
0.015 g each, and 1-5 × 10 ⁻⁵ mol
/ L dye (CI Acid O)
range 7) and 200m of 0.1M acetate buffer at pH5
was placed in a glass bottle and subjected to adsorption treatment at 30 ° C. with stirring. After 72 hours, a part of the solution was centrifuged, and the supernatant was colorimetrically measured at 486 nm, the free dye concentration was measured, and the adsorption rate ( %) Was calculated. The results are shown in (Table 9).

[0043]

[Table 9]

Example 10 As a processed beer cake, 5.0 g of a dried MPF fraction and 0.5 g of a dried MPF fraction were used.
02 mol of triacryloylhexahydro-1,3,3
5-s-triazine (Daito Chemical Co., Ltd.)
Suspended with 200 ml of H11 sodium carbonate buffer, 8
A crosslinked MP prepared by heating at 0 ° C. for 90 minutes, filtering, washing sufficiently with acetone, and drying / crushing.
F-2 was used. As controls, crosslinked husk-2 obtained by crosslinking the dried barley husk fraction in the same manner as described above, and pH 1
Crosslinked husk-3 prepared in the same manner as described above except that the sodium carbonate buffer of No. 1 was replaced with a sodium phosphate buffer of pH 11 [0.1 M- (Na ₂ HPO ₄ + NaOH)] and heated at 90 ° C. Using. Crosslinked MPF-2, Crosslinked husk-
2, 0.015 g each of crosslinked husk-3,
A dye (CI Acid Orange 7) adjusted to a concentration of 10 × 10 ⁻⁵ mol / L and 0.1M-pH5
200 ml of an acetate buffer was placed in a glass bottle and subjected to adsorption treatment at 30 ° C. with stirring. After 72 hours, a part of the solution was centrifuged, and the supernatant was colorimetrically measured at 486 nm to measure the free dye concentration. The adsorption rate (%) was calculated. The results (Table 1
0).

[0045]

[Table 10]

As is evident from the results of Examples 1 to 10, when the beer cake or the processed product of the beer cake is brought into contact with a metal compound or a dye, the metal ions or the dye which has been dissolved can be effectively dissolved. It can be adsorbed on the cake residue.

[0047]

According to the present invention, metals and / or dyes / pigments in wastewater can be economically inexpensive, easily handled industrially and easily, and are useful as fertilizers, feeds and feeds. It is possible to obtain a beer meal to which metal ions are adsorbed or a processed product thereof.

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Claims (7)

[Claims] 1. A solution containing a metal compound and / or a dye / dye is brought into contact with beer lees or a processed product thereof, and metal ions and / or dyes / dyes in the solution are adsorbed on the beer lees or the processed product thereof. A method for treating a metal compound and / or a dye / pigment-containing solution with beer meal or a treated product thereof. 2. A solution of a metal compound and / or a dye / dye-containing solution obtained from beer cake or a processed product thereof according to claim 1, wherein the solution containing the metal compound and / or the dye / dye is wastewater. Processing method. 3. The beer lees or the beer lees according to claim 1, wherein the processed beer lees is a processed beer lees processed so that the protein content is 40% or more. A method for treating a metal compound and / or a dye / pigment-containing solution with a treated material. 4. The processed beer lees processed by a cross-linking treatment with a cross-linking agent is used as the processed beer lees, the beer lees or the metal compound obtained from the processed product thereof. Alternatively, a method for treating a dye / pigment-containing solution. 5. A beer lees or a processed product thereof adsorbing metal ions, wherein a solution containing a metal compound is brought into contact with a beer lees or a processed product thereof. 6. The processed beer cake has a protein content of 40.
% Beer lees adsorbed with metal ions or a processed product thereof, characterized in that it is a processed beer lees processed so as to be at least 0.1%. 7. The beer grain adsorbed with metal ions or the processed product thereof according to claim 5 or 6, wherein the processed beer grain is a processed beer grain processed by a crosslinking treatment with a crosslinking agent.