JP6397196B2 - Method for reducing electrical conductivity for growing soil - Google Patents

Description

The present invention relates to a method for chemically reducing the electrical conductivity of soil in order to make the soil containing excessive essential elements a growing soil.
Industrially, the present invention is a soil in which essential elements such as tsunami deposit soil are excessive (the electrical conductivity exceeds the target value of the Port Authority Greenery Planting Design and Construction Manual, April 1999). The present invention relates to a method for chemically reducing soil) to an electrical conductivity that easily becomes a target value of the Port Authority of the Ministry of Transport on an industrial scale.
The present invention interacts the action of a water-soluble polymer (especially agglomeration) and the chemical action of a water-soluble polymer due to a cation bond having a valence of 2 or more to make a soil containing excess essential elements a growing soil. The present invention relates to a method for reducing electrical conductivity.

<About electrical conductivity of growing soil>
In forest growth, nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), oxygen (O), hydrogen (H), carbon (C), magnesium (Mg), sulfur (S), iron Essential elements of (Fe), manganese, (Mn), boron (B), zinc (Zn), molybdenum (Mo), copper (Cu), and chlorine (Cl) are collected from the growing soil.
If the essential elements of the growing soil are excessive, forest growth becomes difficult. The Ministry of Transport, Port Bureau shows the target value of electrical conductivity mS / cm suitable for growing soil. According to the target value of the Port Authority of the Ministry of Transport, the electrical conductivity suitable for growing soil is 1.5 mS / cm or less, the upper effective soil layer is in the range of 0.1-1.0 mS / cm, and the lower effective soil layer is 1.5 Less than mS / cm is accepted and forest growth is optimized in the area of their electrical conductivity.

On the other hand, the soil in the affected areas often contains a lot of metal waste materials, etc., so that the nutrient element ions become excessive and the electrical conductivity dS / m increases (that is, the salt concentration increases). The water retention, ventilation, and water permeability of the soil become poor, making it unsuitable for growing soil. When the upper effective soil layer is 1.0 dS / m or more and the lower effective soil layer is 1.5 dS / m or more, it is not suitable as a growing soil in which the forest grows.
Electrical conductivity is the target value for the growing soil.
According to JGS0212-2000, electrical conductivity dS / m (mS)
/ cm) measurement method.

<Use of water-soluble polymers in civil engineering work>
In civil engineering works, the use of synthetic and natural water-soluble polymers has been proposed (see Patent Documents 1 to 3). According to Patent Document 1, fine particles having electric charge contained in waste are chemically bonded with a water-soluble polymer, and the waste can be separated into a size that can be sieved in a water-containing state.

Patent Document 2 is a water-soluble polymer for imparting fluidity such as sand to recycle soft or highly sticky water-containing soil for backfilling, etc., and to solidify it to such an extent that it does not swell in water. Is used.
In Patent Document 3, excavated soil having a high water content (water content of about 20 to 90%) generated by tunnel construction and others is coagulated and solidified with a water-soluble polymer to form a solid form that can be discarded. .

Since Patent Documents 1 to 3 are based on solidification of hydrous soil, Patent Document 1 uses cement, gypsum, quicklime, and magnesium oxide in combination, and Patent Document 2 uses lime, quicklime, or slaked lime, In Patent Document 3, slaked lime, cement-based additive, and Portland cement are used in combination.

JP 2012-176394 Japanese Patent Laid-Open No. 4-345685 JP 63-44097

Supervised by Kimihiko Noda; “Fundamental and Applied Technology of Water-soluble Polymers” published in 2009 CMC Publishing Co., Ltd.

≪Utilization of water-soluble polymers in conventional civil engineering works≫
(1) Civil engineering works mainly include dredging work, excavation work, muddy water treatment, and the use of water-soluble polymers in soft soil solidification. , Protective colloids, thickeners and emulsion stabilizers.
For that reason, in dredging work, draining by reducing the turbidity of the water in the construction,
Nonionic polyvinyl acrylamide and copolymers thereof, anionic and cationic water-soluble polymers, are frequently used (see, for example, Non-Patent Document 1).
(2) In excavation work or the like, the protective colloid action of polyvinyl alcohol, methylcellulose and polysaccharides is utilized to stabilize mud (see Non-Patent Document 1, for example).
(3) Polyvinyl alcohol, water-soluble polyurethane, sodium alginate, and polysaccharides are used as a polymer solidifying agent in a solidification treatment with soft soil (for example, see Non-Patent Document 1).
(4) The use of water-soluble polymers in conventional civil engineering works is mainly for solidification of hydrous soil such as dredging, excavation, and muddy water treatment. There is no idea or suggestion of the present invention such as use in the reaction.
≪Problems in creating the present invention≫

(1) The conventional method of making soil with excessive essential elements (such as tsunami-deposited soil) as growing soil is an agricultural measure such as reducing fertilizer and adding new soil.
(2) Agricultural high salt removal from soil with excessive essential elements to growing soil is substantially difficult economically and technically.
(3) Therefore, the present inventor has studied in detail the chemical methods such as the combination of the water-soluble polymer-derived aggregating, adsorbing and solidifying functions and the water-soluble polymer's reactivity. The invention has been found.
<< The electric conductivity reducing method of the present invention has the following objects. ≫

(A) It is an object of the present invention to provide a method for reducing the electrical conductivity of soil containing excessive essential elements to the electrical conductivity of growing soil by a chemical method.
(B) An object of the present invention is to provide a method for reducing the essential element from a soil containing excess essential elements to a desired electrical conductivity of growing soil by selecting a water-soluble polymer.
(C) The present invention provides a method for reducing the electrical conductivity of growing soil, even if it is a concentration disorder occurring in soil of any condition such as plain land, embankment or complex morphological soil of tsunami deposit soil. Objective.
(D) It is an object of the present invention to provide a method for easily reducing the electrical conductivity of soil grown on an industrial scale from soil containing excessive essential elements.

(E) An object of the present invention is to provide a method for reducing electrical conductivity for growing soil that is economically significant by utilizing existing industrial products (water-soluble polymers and inorganic compounds).

The electrical conductivity reduction method for making the growing soil of the present invention (the present invention according to claim 1) is an excess of essential elements, a water content of 20 to 90% by weight, and an electrical conductivity of more than 1.5 mS / cm. the inorganic compound and a water-soluble polymer which releases the water-soluble cationic and added to the soil, reducing the soil involves a water-soluble polymer to the hydrophobic by binding of the water-soluble cationic and the water-soluble polymer The processing is performed .

According to the present invention, the following effects (i) to (vii) can be enjoyed.
(I) Growing soil that satisfies the target value of electrical conductivity for the growing soil of the Port Authority of the Ministry of Transport is easily obtained.
(Ii) Growing soil that satisfies the target value of electrical conductivity related to the growing soil of the Port Bureau of the Ministry of Transport and has the desired electrical conductivity can be easily obtained.
(Iii) Since the electrical conductivity reduction treatment for soil with excess essential elements is based on basic operations such as mixing of soil, basic industrial chemicals, and water systems, even in complex forms of flat land, embankment or tsunami deposit soil Easy.
(iv) The reduction conditions can be easily changed by changing the quantitative ratio of the water-soluble polymer and the inorganic compound that releases a water-soluble cation having a valence of 2 or more.

(V) Since the electrical conductivity of the growing soil is reduced by a small number of basic chemicals, it can be easily reduced on an industrial scale.
(Vi) Since a small number of existing basic industrial chemicals (water-soluble polymers and water-soluble inorganic compounds) are used, the electrical conductivity can be reduced at a low cost.

(Vii) It is easy to construct large-scale construction of growing soil by reducing electrical conductivity.

These are explanatory drawings schematically showing a chemical process leading to a growing soil by interacting with a water-soluble polymer and a cation with respect to a soil in which essential elements are excessive.

<< Specific Outline of Embodiments of the Present Invention >>

(A) <Specific description of electric conductivity reduction method>

The method for reducing the electrical conductivity of the growing soil according to the present invention will be specifically described based on Example 2.
(1) The present invention releases a water-soluble polymer ( Example 2: polyacrylic acid Na 2) and a water-soluble cation having a valence of 2 or more with respect to soil containing excess essential elements (Example 2: Tsunami-deposited soil). An inorganic compound ( Example 2: hemihydrate gypsum CaSO ₄ · 1 / 2H ₂ O ) is added and reduced to a composite.
The tsunami deposit soil of Example 2 has a wet density of 1.640 t / m ³ . The wet density cannot be directly converted to the moisture content% of the hydrous soil, but is approximately 30 to 50% moisture content.

In soil with excessive essential elements (Example 2: Tsunami deposited soil), the following chemical phenomenon will inevitably progress as time passes.
A high-molecular-weight water-soluble polymer (Example 2: polyacrylic acid Na) dissolves in the moisture of the soil in which the essential elements are excessive (Example 2: Tsunami sedimentary soil) to become a viscous aqueous solution, Adsorption, adhesion, and intrusion into the surface, surroundings, and gaps of soil particles and soil particle groups causes condensation, aggregation, and solidification (see (1) and (2) in Fig. 1).
A viscous aqueous solution in which a water-soluble polymer is dissolved often comes into contact with the surface of soil particles and soil particle groups, so it is presumed that agglomerated and aggregated aggregates will increase (see (3) in Fig. 1). . Although FIG. 1 is based on observations in many experiments, various forms of hybrids including a solidified state are produced, but many of them have the form (3) in FIG.
In addition, the “hybrid” of the present invention is used in the sense of a product produced from different components (water, soil particles, soil particle group, water-soluble polymer, etc.).

The water-soluble polymer of the present invention binds to a water-soluble cation having a valence of 2 or more to become hydrophobic .

In Example 2 of the present invention, divalent water-soluble cation Ca ions dissociated from hemihydrate gypsum calcium sulfate moved through the water-soluble polymer-dissolved viscous aqueous solution, and the surfaces and surroundings of soil particles and soil particles. The phenomenon of entering and adhering to the gap and binding to the water-soluble polymer (Example 2: polyacrylic acid Ca) covering the hybrid inevitably proceeds.
In the case of Example 2, since the water-soluble polymer is in the form of a salt of polyacrylic acid Na, Ca ions and polyacrylic acid Na become polyacrylic acid Ca by a substitution reaction. Since the polyacrylic acid Ca is hydrophobic, the water-soluble polymer that has entered, adhered to, or covered the soil particles and the soil particle group becomes hydrophobic and is integrated by aggregation or the like. The interior also becomes hydrophobic.
When the water-soluble polymer is polyacrylic acid, Ca ions and polyacrylic acid react to form polyacrylic acid Ca, and the same effect is obtained.
(B) <Reduction experiment of electrical conductivity of tsunami-deposited soil with hydrophobized water-soluble polymer>

In a transparent plastic container having a depth of 20 cm and a diameter of about 30 cm, the experiment for reducing the electric conductivity of Example 2 was performed, and a hybrid was produced under the same conditions as the constituent element (A) of the present invention. The water-soluble polymer was polyacrylic acid Na, and the inorganic compound producing a divalent water-soluble cation was hemihydrate gypsum CaSO ₄ .1 / 2H ₂ O).
When the transparent plastic container was observed after about 30 minutes, the coagulation and agglomeration of the hybrid were observed (see Fig. 1). The aggregate surface was covered with a condensed layer of a viscous aqueous solution of water-soluble polymer. The electrical conductivity of the water-soluble polymer-dissolved viscous aqueous solution was close to that of Example 2. The electrical conductivity increased when the condensed layer on the surface of the aggregate was broken. The condensed layer on the surface of the aggregate was not broken under normal conditions.
(C) <Auxiliary material used in the present invention>

While water-soluble polymers and inorganic compounds that release divalent or higher water-soluble cations are essential materials, hemihydrate gypsum (CaSO ₄ 1 / 2H ₂ O The undissolved portion in water absorbs water and becomes CaSO ₄ · 2H ₂ O, which acts as a strong flocculant. When the insoluble component in water works as a strong flocculant (for example, gypsum), the effect of the present invention is synergistically imparted, so that the insoluble component is also used.
(D) <Synthetic water-soluble polymer used in the present invention>

(1) The synthetic water-soluble polymer used in the present invention is preferably one having excellent aggregation properties.
As the synthetic water-soluble polymer, those exemplified in the following (a) to (d) are suitable. However, in cases other than the following (a) to (d), when the efficiency of the effect of the invention is not emphasized,
It can be used.
(A) Use of polyacrylic acid, polymethacrylic acid and salts thereof. As the salt, for example, polyacrylic acid Na, polymethacrylic acid Na and the like are suitable.
(B) Use of a copolymer of acrylic acid or methacrylic acid and acrylamide. The same applies to a copolymer of polyacrylic acid Na and polyacrylamide.
(C) Use of polyalkylamino-based salts of polyalkylaminoacrylates and polyalkylaminomethacrylates.
(D) Use of a methacryloxyethyltrimethylammonium chloride polymer and a copolymer of alkylaminoacrylate and acrylamide. The copolymer is a copolymer of acrylamide and acryloyloxymethylammonium chloride.
When a plurality of synthetic water-soluble polymers are used, they may be selected from the same type or different types of water-soluble polymers.

(2) Synthetic water-soluble polymers include oligomeric polymers, but those used in the present invention have molecular weights of one million, several million, and ten million or more. . A large molecular weight is effective for hydrophobization.
(E) <Natural water-soluble polymer used in the present invention>

(1) The natural water-soluble polymer is preferably a natural polysaccharide or a modified compound of the natural polysaccharide because of its affinity with water-containing soil.
(2) As the natural polysaccharide, for example, guar gum, sodium alginate, locust bean gum, tamarind needum, psyllium needum, xanthan gum, gum arabic and the like are suitable.
(3) For example, cationized guar gum, carboxymethylcellulose sodium salt, etc. are suitable for use as the modified compound of natural polysaccharide.
Natural water-soluble polymers can also be selected from the same species or different species.
(F) <Inorganic compound releasing divalent or higher water-soluble cation>

As the inorganic compound that releases a divalent or higher cation, for example, water-soluble inorganic salts are preferably used, and examples thereof include hydroxides, sulfates, and nitrates. As the hydroxide, for example, calcium hydroxide or magnesium hydroxide is preferably used. Sulfate is, for example, hemihydrate gypsum (CaSO ₄ · 1/2 ) Is preferred.
Aluminum hydroxide can be used to release trivalent aluminum ions. Iron compounds can also be used to release trivalent or higher cations.
(G) <Soil subject to reduction treatment of the present invention>

The soil for which the electrical conductivity of the present invention is to be chemically reduced is a soil that is not suitable for growing soil due to an excess of essential elements. Typically, the soil has an electrical conductivity of more than 1.5 mS / cm , the upper effective soil layer is 1.0 mS / cm above, and the lower effective soil layer is more than 1.5 cm. Even if the soil is below their electrical conductivity, some forests may have optimal growth conditions for lower electrical conductivity. Such a case is also included in the scope of the present invention.

(1) In the present invention, if the growth soil is 1 m ³ , the inorganic compound releasing a water-soluble cation having a valence of 2 or more is 0.5 to 50 parts by weight, and the water-soluble polymer is 0.01 to 5.0 parts by weight. Is easy.
The reason why the upper limit amount of the inorganic compound is large is that the amount of water-soluble cation released in the inorganic compound may be small and they cannot be separated in advance.
(2) Soil with an excess of essential elements can have a moisture content of 20 to 90% by weight. However, when the reduction method of the present invention is performed on soil having an excessive amount of essential elements having a water content of 30 to 60% by weight, it is easy to obtain the target electric conductivity (mS / cm) .
(3) In the present invention, in principle, powder is suitable for the water-soluble polymer and inorganic compounds and auxiliary materials that release divalent or higher cation.

EXAMPLES Next, although an Example demonstrates this invention, an Example is an illustration and is not restrained by the range.

[Experiment to confirm the properties of tsunami-deposited soil]
In Example 1, an experiment for confirming characteristics when only hemihydrate gypsum was added using “tsunami deposited soil” as an object of Examples of the present invention following Example 2 was performed.
The wet density of the tsunami-deposited soil A was 1.640 t / m ^{3 as} measured by the soil wet density test (JGS0191-2000). The amount of material added in this example is the amount of material added to this wet density sample (1 m ³ ).
Table 1 shows the electrical conductivity and pH when hemihydrate gypsum was added to the tsunami sedimentary soil A used in this example.
The electric conductivity was measured by the electric conductivity test method (JGS0212-2000) of the soil suspension. The electrical conductivity meter used was CM-31P manufactured by Toa Decay.
The pH was measured by a soil suspension pH test (JGS0211-2000). As the pH meter, HM-30P manufactured by Toa Decay Co., Ltd. was used. A normal mixer was used to mix the tsunami sedimentary soil with hemihydrate gypsum.
A-1 is the result of testing a mixture of hemihydrate gypsum 25 kg / m ³ .
A-2 is the result of testing a mixture of hemihydrate gypsum 40 kg / m ³ .
A-3 is the result of testing a mixture of hemihydrate gypsum 50 kg / m ³ .

Note 1: Soil A-1 to A-3 of the electric conductivity EC, the dissolution amount of the water of 0.24 g / 100 cm ³
This is the total electrical conductivity of the portion corresponding to 25-50 kg / m ³ and the tsunami sediment.
2: The soils A-1 to A-3 in Table 1 are rejected because the electrical conductivity is 1.52 dS / m or more.
3: In soil A-1 to soil A-3, since the water-soluble polymer is not blended, the effect of the present invention is not obtained.

[Experiment on reducing electrical conductivity of tsunami-deposited soil]
The gypsum used in Example 2 is hemihydrate gypsum, and the water-soluble polymer is sodium polyacrylate. Table-2 shows the results of reducing the electrical conductivity of the tsunami sediment soil A with this material.
Soil A-4 is the result of testing tsunami-deposited soil A mixed with 25 kg / m ³ of 24 kg / m ^{3 of} hemihydrate gypsum and 1 kg / m ³ of sodium polyacrylate.
Soil A-5 is the result of testing tsunami-deposited soil A mixed with 39 kg / m ^{3 of} hemihydrate gypsum and 1 kg / m ³ of sodium polyacrylate, for a total of 40 kg / m ³ .
Soil A-6 is the results of testing that mixed the total 50 kg / m ³ of hemi gypsum 49kg / m ³ and sodium polyacrylate 1 kg / m ³ to tsunami deposits soil A.

Note 1: Soil A-4 to A-6 are acceptable when the electrical conductivity is 1.5 dS / m or less of the lower effective soil layer in terms of dS / m. Soil A-6 is acceptable at 1.0 dS / m or less of the upper effective soil layer.

[Experiment to reduce electrical conductivity of tsunami-deposited soil]
The gypsum used in Example 3 is hemihydrate gypsum, and the water-soluble polymer is poly (sodium acrylate) acrylic amide copolymer.
Soil A-7 is the result of testing that mixed the hemi gypsum 24 kg / m ³ and a total 25 kg / m ³ of sodium acrylate acrylamide copolymer 1 kg / m ³ to tsunami deposits soil A.
Soil A-8 is the result of testing tsunami-deposited soil A mixed with 39 kg / m ^{3 of} hemihydrate gypsum and 1 kg / m ³ of sodium acrylate acrylate amide copolymer for a total of 40 kg / m ³ .
Soil A-9 is the result of testing that mixed the hemi gypsum 49kg / m ³ and a total 50 kg / m ³ of sodium acrylate acrylamide copolymer 1 kg / m ³ to tsunami deposits soil A.

Note 1: Soil A-7 to 9 passes the lower effective soil layer at 1.5 dS / m or less. Soil A-8-9 passes with 1.0 dS / m or less of an upper effective soil layer.
2: Soil A-7-9 has the most excellent reduction rate of electrical conductivity compared with another Example.

[Experiment to reduce electrical conductivity of tsunami-deposited soil]
The gypsum used in Example 4 is hemihydrate gypsum, and the water-soluble polymer is a guar gum copolymer. Table 4 shows the results of reducing the electrical conductivity of the tsunami-deposited soil A with this material.
Soil A-10 is the result of testing that mixed the total 25 kg / m ³ of hemi Gypsum 24 kg / m ³ and guar gum 1 kg / m ³ to tsunami deposits soil A.
Soil A-11 is the results of testing that mixed the total 40 kg / m ³ of hemi Gypsum 39 kg / m ³ and guar gum 1 kg / m ³ to tsunami deposits soil A.
Soil A-12 is the results of testing that mixed the total 50 kg / m ³ of hemi gypsum 49kg / m ³ and guar gum 1 kg / m ³ to tsunami deposits soil A.

Note 1: Soil A-10 to A-12 passed the lower effective soil layer at 1.5 dS / m or less.
It should be noted that modifications or partial changes and additions are optional and are within the scope of the present invention as long as they are suitable for the present invention and do not particularly impair the effects of the present invention.

In the past, there was no effective way to make vegetable soils in tsunami-deposited soils and other high-salt disaster soils. However, it becomes economically and technically possible to make the soil vegetable by the method of the present invention.

Claims (3)

Essential soil excess, moisture content 20-90% by weight, and soil with electrical conductivity exceeding 1.5mS / cm, mixed with inorganic compounds that release divalent or higher water-soluble cations and water-soluble polymers , reduction of electrical conductivity for the growing soil, characterized in that, to carry out the reduction process involves the hydrophobic water-soluble polymer by conjugation with a water soluble cation and said water-soluble polymer. The reduction treatment involving making the water-soluble polymer hydrophobic is 0.01 to 5 parts by weight of the water-soluble polymer and 0.5 to 50 parts by weight of the inorganic compound that releases water-soluble cations per 1 m ³ of the growing soil. The method for reducing electrical conductivity for obtaining the growing soil according to claim 1, wherein: 2. The method for reducing electrical conductivity for obtaining a growing soil according to claim 1, which has at least one of the following characteristics (a) to (c).
(A) As said water-soluble polymer, polyacrylic acid, polymethacrylic acid, acrylic acid or a copolymer of methacrylic acid and acrylamide, polyacrylic acid Na, polymethacrylic acid Na, polyacrylic acid Na and polymethacrylic Copolymer of acid Na, polyalkylaminoacrylate, polyalkylamino water-soluble polymer of polyalkylaminomethacrylate salt and methacryloyloxyethyltrimethylammonium chloride polymer, copolymer of alkylaminoacrylate and acrylamide Synthetic water-soluble polymers are used.
(B) The water-soluble polymer is selected from the same species or different species.
(C) As the inorganic compound, a water-soluble inorganic salt, hydroxide, or sulfate is used.