JPH11293227A - Agent for solidifying water-soluble organic matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agent which, even when added in a small amount, can solidify aqueous sludge, waste liquors from fermentation and brewing processes even when they have a low solid matter content by combining an alkaline earth metal oxide with a highly water-absorbing polymer and/or an agglomerant. SOLUTION: The alkaline earth metal oxide is preferred to be a powdery one on account of its easy handleability and improved reactivity. It is generally calcium oxide or magnesium oxide, which is easily handleable and is effective to inhibit the solidified product from being re-dissolved in water. The highly water-absorbing polymer is exemplified by an ionic highly water-absorbing polymer such as a crosslinked polyacrylate or a nonionic highly water-absorbing polymer such as a crosslinked poly-N-vinylcarboxylic acid amide, and the latter is more effective. The agglomerant may be a polymeric one or an inorganic one. It is desirable that 5-50 pts.wt. highly water-absorptive polymer and/or agglomerant are used per 100 pts.wt. alkaline earth metal oxide powder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solidifying agent for a water-soluble organic substance, and more particularly to a solidifying agent for solidifying a water-soluble organic substance such as aqueous sludge, waste liquid of a fermentation brewery production process or aqueous paint waste liquid. .

[0002]

2. Description of the Related Art For example, water-based sludge and water-based paint (washing)
Since the waste liquid is water-soluble, when it is discarded, if it is discarded as it is, it causes water and soil pollution of the river. Therefore, when the aqueous paint washing waste liquid is discarded, it is necessary to separate the water and the pigment component and the organic component using a waste liquid treatment facility. In a painting factory or a painting site that does not have a waste liquid treatment facility, the treatment cannot be performed, which causes a trouble that pollutes water quality and soil. On the other hand, in wastewater from the shochu production process and sake liquor production process, that is, the wastewater from the fermentation brewery production process, 600 tons or more of wastewater is dumped into rivers and seas per month, but it is difficult due to stricter legal regulations. These waste liquids are vacuum-distilled to separate water.

[0003]

However, in the method of separating aqueous sludge and aqueous paint waste liquid, when the liquid waste is discarded as it is, the separated water contains organic components such as resin, and it is not easy to use it after purification. Can not be disposed of. At present, the pigment cannot be disposed of unless the water content is 85% or less. A method for separating water by vacuum distillation of a waste liquid of a shochu production process and a waste liquid of a sake production process includes an organic substance such as alcohol in the separated water, and a COD (chemical oxygen demand) of, for example, 40000 mg. / L, etc. and cannot be disposed of in rivers. In addition, the distillation residue has a water content of about 60%, becomes a large lump and is difficult to remove from a vacuum still, and remains sticky even when mixed with a conventional solidifying agent such as cement, and is directly discarded as industrial waste. There were problems such as inability to do so.

Accordingly, the present inventors have conducted research to solve the above-mentioned problems in the conventional solidifying agent, and as a result, have found a good solidifying agent for aqueous sludge and wastewater from the fermentation brewery production process, and have completed the present invention. did. The present inventor has previously invented and applied a solidifying agent capable of solidifying within 15 hours by adding 2 parts by weight to a water-based waste paint as a solidifying agent for a water-based paint (see JP-A-8-120254). did. The solidifying agent of this early invention comprises alkaline earth metal oxide powders 40 to 9
It contains 0.1 to 60 parts of the superabsorbent polymer powder with respect to 9.9 parts by weight (hereinafter simply abbreviated as "part"), so that the aqueous waste paint can be made into a coarse solid state. However, at the time of use, when the components (activator, alcohol, etc.) contained in the aqueous waste paint and the paint concentration were low, the water absorption performance was different, and the solidification state was uneven.

Accordingly, an object of the present invention is to further improve the above-mentioned initial invention, and to provide an aqueous system which can be solidified even with a smaller addition amount than the solidifying agent of the initial invention and even when the solid content is small. It is an object of the present invention to provide a solidifying agent for sludge, waste liquid of a fermentation brewing product manufacturing process, or aqueous paint waste liquid.

[0006]

According to a first aspect of the present invention, there is provided a solidifying agent for an aqueous sludge, wherein a solidified product is not dissolved in an aqueous liquid, and an alkaline earth metal oxide is formed. And a superabsorbent polymer and / or a flocculant.

[0007] In order to solve the above-mentioned problems, the solidifying agent for the waste liquid of the fermentation brewery production process according to the second aspect of the present invention is characterized in that the solidified product does not dissolve in an aqueous solution, and that an alkaline earth metal oxide is formed. , A superabsorbent polymer and / or a flocculant.

[0008] In order to solve the above-mentioned problems, the solidifying agent for aqueous paint waste liquid according to the third aspect of the present invention is characterized in that the solidified product does not dissolve in the aqueous liquid, and the alkaline earth metal oxide and the nonionic high-pressure liquid do not dissolve. It is characterized by comprising a water absorbing polymer and / or a flocculant.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The aqueous liquid is water, an alcohol liquid,
Alternatively, it refers to an aqueous liquid having an OH group (aqueous medium), and may be an aqueous sludge, a waste liquid of a fermentation brewery production process, a liquid containing an aqueous paint, or a liquid itself excluding these.

The alkaline earth metal oxide easily undergoes a hydration reaction with water and absorbs water, so that the water-soluble organic substance thickens and solidifies with time to become insoluble. It is preferable to use a powder in order to improve ease of handling and reactivity.
As the alkaline earth metal oxide, calcium oxide and magnesium oxide are common and easy to use, and have an effect of preventing the solidified product from being redissolved by water.

The superabsorbent polymer includes a crosslinked polyacrylate, a crosslinked polymethacrylate, a crosslinked polyacrylamide hydrolyzate, a crosslinked acrylic acid-acrylamide copolymer, a crosslinked vinyl ester Saturated carboxylic acid copolymer saponified product, crosslinked acrylic acid-acrylate copolymer, crosslinked sulfonated polystyrene, crosslinked sodium carboxymethylcellulose, crosslinked starch-polyacrylonitrile graft copolymer hydrolyzate, crosslinked Starch-
Sodium polyacrylate graft polymer, cellulose-sodium polyacrylate, cross-linked isobutylene-
An ionic superabsorbent polymer such as an alkali neutralized maleic anhydride copolymer, a polyoxyethylene chain-containing urethane, or a self-crosslinking polyacrylate is applied.
As the superabsorbent polymer, a nonionic superabsorbent polymer such as cross-linked poly N-vinyl carboxylic acid amide, cross-linked polyethylene oxide, or cross-linked polyvinyl alcohol is used.

The water absorption of the ionic superabsorbent polymer is due to the affinity for water and the osmotic pressure due to the higher ion concentration inside the polymer than outside. When the ion concentration outside the polymer (water) is high or when a small amount of a hydrophobic substance is present, the water absorption of water-soluble organic substances is significantly reduced. On the other hand, the water absorption of the nonionic superabsorbent polymer is hardly affected by the ion concentration of water, the contained hydrophobic substance, and the water-soluble organic substance. The nonionic superabsorbent polymer having high water absorbency is a polymer such as poly N-vinyl carboxylic acid amide, polyethylene oxide, and polyvinyl alcohol, and is used for aqueous sludge, waste liquid for fermentation brewery production process, or aqueous paint waste liquid. Especially effective.

The flocculant includes sodium alginate,
Carboxymethylcellulose sodium salt, sodium polyacrylate, partially hydrolyzed salt of polyacrylamide, maleic acid copolymer, water-soluble aniline resin, polythiourea, polyethyleneimine, quaternary ammonium salt,
Polymeric flocculants such as polyvinylpyridines, polyacrylamide, polyoxyethylene, and caustic starch; inorganics such as aluminum sulfate, polyaluminum chloride, sodium aluminate, iron sulfates II and III, iron (III) chloride, chlorinated coppers It is a flocculant.

According to tests, a good solidifying agent can contain 0.1 to 100 parts of a superabsorbent polymer and / or a coagulant per 100 parts of alkaline earth metal oxide powder. When the amount of the superabsorbent polymer and / or the coagulant is 0.1 part or less, there is no water absorption effect and no coagulation effect. Therefore, it cannot be solidified uniformly. The amount of the superabsorbent polymer and / or flocculant is preferably in the range of 5 to 50 parts. Superabsorbent polymers and flocculants can be used equally.

The water-soluble organic substance to which the present invention is applied is aqueous sludge (organic sludge), waste liquid of a fermentation brewed product such as shochu or sake, or waste liquid of aqueous paint. The waste liquid may be a disposal product of the product itself or an unnecessary product. Further, the waste liquid contains a water-soluble organic component, but may contain a hydrophilic organic component.
The hydrophilic organic component can be solidified.

As the solidifying agent, if necessary, an extender pigment, an aggregate,
Water-absorbing inorganic substances, water-absorbing organic substances, and the like can be blended.

As extenders, calcium carbonate, sodium carbonate, precipitated barium sulfate, clay, talc and the like can be used as extenders. The blending amount of the extender is 60 parts or less, preferably 1 to 30 parts. If the extender exceeds 60 parts, a predetermined solidification effect cannot be obtained.

Examples of the aggregate include silica sand, cold water stone, ceramic fine granules, colored sand, and lightweight aggregates (such as perlite and vermiculite). The amount of the aggregate is 30 parts or less, preferably 1 to 20 parts. When the amount of the aggregate exceeds 30 parts, a good solidification effect cannot be obtained.

The water-absorbing inorganic substances include bentonite, zeolite, acid clay, molecular sieve, silica gel, alumina gel, porous glass, diatomaceous earth and the like. The amount of the water-absorbing inorganic substance is 20 parts or less, preferably 1 to 10 parts. If the water-absorbing inorganic substance exceeds 20 parts, the miscibility with the water-soluble organic substance is reduced.

The water-absorbing organic substance is for making solidification of the water-soluble organic substance advantageous, and a water-absorbing material such as sawdust and bran can be used.

Sawdust is a wood cutting such as cedar and cypress. Sawdust is partially reused, but mostly discarded. Bran is generated when threshing rice. By utilizing the water absorption of sawdust and bran, the amount of the superabsorbent polymer can be reduced, and the processing cost can be reduced. The amount of the water-absorbing organic substance such as sawdust and bran is 40 parts or less, preferably 5 to 30 parts.
If the water-absorbing organic substance exceeds 40 parts, the miscibility with the water-soluble organic substance decreases.

[0022]

Next, embodiments of the present invention will be described. First, eleven solidifying agents are prepared as examples of the present invention. That is, each of the solidifying agents of Examples 1 to 11 was manufactured by mixing the respective raw materials in the composition shown in Table 1. In addition, the numerical unit in Table 1 is a part.

The raw materials used are as follows. Calcium oxide is calcium oxide manufactured by Maruo Calcium Co., Ltd.
Crosslinked superabsorbent polymer is manufactured by Showa Denko KK NV
ANA010 (nonionic poly N-vinyl carboxylic acid amide) and polyacrylamide as the flocculant of Examples 5, 8, and 9 were Alonfloc A1 manufactured by Alonfloc Co., Ltd.
66, the polyaluminum chloride of the coagulant of Examples 6 and 10 was obtained by using powdered polyaluminum chloride manufactured by Oji Paper Co., Ltd., and the aluminum sulfate of the coagulant was manufactured by using a powder band manufactured by Oji Paper Co., Ltd. Was prepared by mixing the respective raw materials in the respective formulations shown in Table 1.

[0024]

[Table 1]

Next, as comparative examples for the solidifying agents of Examples 1 to 11, Comparative Examples 1 and 2 made of the material described in JP-A-8-120254 of the earlier invention and Comparative Examples of a conventional product made of Portland cement 3 and Comparative Example 4 of a conventional product made of a superabsorbent polymer. As the magnesium oxide of Comparative Examples 1 and 2, magnesium oxide manufactured by Sobueclay Co., Ltd. was used. The compositions of Comparative Examples 1, 2, 3, and 4 are as shown in Table 2. The numerical unit in Table 2 is part.

[0026]

[Table 2]

A waste liquid was used as the water-soluble organic substance used in the solidification test. The waste liquid 1 was a washing waste liquid of a water-based paint Rafton EM enamel manufactured by Suzuka Fine Co., Ltd. The waste liquid 2 was a waste liquid generated in a shochu manufacturing process. Table 3 shows the adjustment of each waste liquid.
Shown in

[0028]

[Table 3]

Next, the solidifying agents of Examples 1 to 11 and Comparative Examples 1 to 4 were added to the aqueous paint washing waste liquid and the waste liquid of the shochu manufacturing process, respectively, at an external ratio of 10% and 20%, respectively, to evaluate the solidifying effect. . The results are as shown in Table 4.

[0030]

[Table 4] Evaluation was conducted by adding a solidifying agent, and after stirring, ◎ was within 30 minutes, が was within 2 hours, □ was 1-2 days, Δ was 3 to 7 days, and × was not solidified after 7 days. .

With respect to Examples 5 to 11 containing a coagulant, the effect of coagulating and sedimenting a suspension of an organic substance, an inorganic substance or the like and separating the suspension from water was tested. The addition amount was 0.5%, 3%, and 5% of the waste liquid. The results are shown in Table 5.

[0032]

[Table 5] Evaluation was performed by adding a solidifying agent, and after stirring, ◎ was within 1 hour, ○ was within 4 hours, □ was 1 to 2 days, Δ was 3 to 7 days, and completely separated into two layers of water and sediment. However, the water was still cloudy 7 days later.

The water and precipitate completely separated into two layers could be separated by decantation or filtration. From this, it was recognized that the precipitate can be solidified by adding 1 to 5% of the solidifying agent. In addition, this demonstrates that the amount of waste can be reduced by removing water.

In Examples 1 to 11, compared with Comparative Examples 1 to 4, water-based paint washing effluent and shochu manufacturing process effluent could be added in a small amount and solidified earlier, and the solidified product was more likely to become granular. By mixing the coagulant as in Examples 5 to 11, the amount added was changed, and a coagulant having a coagulation effect and a solidification effect was obtained with one agent. Therefore, Examples 1 to 11 are effective solidifying agents in waste treatment.

In another test, the waste liquid in the sake production process and the disposal of other brewed products were tested in the same manner as in the above-described tests of Examples 1 to 11, and a good solidified product was obtained within one hour. Was. The solidified material is effective as an environmental pollution countermeasure because it does not redissolve in water.

It is to be noted that claims 1 to 3 of the present invention can have the following aspects. 100 parts of alkaline earth metal oxide and 0.1 to 10 of superabsorbent polymer and / or coagulant
The solidifying agent for aqueous sludge according to claim 1, comprising 0 part. The solidifying agent for waste liquid of a fermentation brewery manufacturing process according to claim 2, comprising 100 parts of an alkaline earth metal oxide and 0.1 to 100 parts of a superabsorbent polymer and / or a flocculant. Alkaline earth metal oxide 100
The solidifying agent for aqueous paint waste liquid according to claim 1, comprising 0.1 to 100 parts by weight of a nonionic superabsorbent polymer and / or a flocculant. Even in the case of the above-described embodiment, the solidification of each corresponding water-soluble organic substance can be favorably performed.

[0037]

According to the first aspect of the present invention, for example,
Water-based sludge can be solidified with a small addition amount of 1.5 to 20%. According to the present invention, it is possible to satisfactorily solidify even an aqueous sludge having a small solid content of, for example, 3%. The formed solid is convenient because it does not dissolve in the aqueous liquid.

According to the second aspect of the present invention, for example,
A small amount of 5 to 20% can solidify wastewater sludge of fermentation brewery production process. According to the present invention, for example, 3
% Solids can be satisfactorily solidified even in the waste liquid of the fermentation brewery production process. The formed solid is convenient because it does not dissolve in the aqueous liquid.

According to the invention of claim 3, for example, 1.
The aqueous paint waste liquid can be solidified with a small addition amount of 5 to 20%. According to the present invention, it is possible to satisfactorily solidify even an aqueous paint waste liquid having a small solid content of, for example, 3%. The formed solid is convenient because it does not dissolve in the aqueous liquid.

Claims (3)

[Claims] An aqueous sludge characterized in that a solidified product is not dissolved in an aqueous solution and contains an alkaline earth metal oxide, a superabsorbent polymer and / or a flocculant. Solidifying agent. 2. A fermented brewed product characterized in that the solidified product is insoluble in an aqueous liquid and contains an alkaline earth metal oxide, a superabsorbent polymer and / or a flocculant. A solidifying agent for wastewater from manufacturing processes. 3. An aqueous system, wherein the solidified product is insoluble in an aqueous solution and comprises an alkaline earth metal oxide, a nonionic superabsorbent polymer and / or a flocculant. Solidifying agent for paint waste liquid.