JP2000109838A - Soil improving agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To accelerate propagation of bacteria in soil and increase humification in soil by using a soil improving agent containing a bacteria-removing bed and a silicic acid-based or aluminosilicic acid-based active agent having a specific cation exchange capacity and ammonium adsorption. SOLUTION: An active agent such as a silicic acid-based agent and the like contained in a soil improving agent has cation exchange capacity of not less than 50 meq/100 g. Further, the active agent preferably has water absorption capacity of not less than 15% (measured after being dryed at 110 deg.C for 90 min) and soluble silicic acid component of not less than 6 mg/100 g. A bacteria removing bed to be used is a bacteria bed which was used for cultivating various mushrooms preferably including dyophyllum shimeji mashroom, Collybia veltipes, Pleecrotus ostreatus, Pholiota nameko or Grifola frondasa mushroom and is disposable. The soil improving agent preferably includes 5-100 pts.wt. of the active agent per 100 pts.wt. of the bacteria-removing agent on a dry base (110 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a modifier for soil, in particular to contaminated soil, and more particularly, to a combination of a bactericidal bed and a specific siliceous or aluminosilicate activator. It contributes to the improvement of the magnetic force of the soil, such as increasing the organic components in the soil and increasing the propagation of microorganisms, and can also effectively decompose and remove aromatic halogen compounds and other heavy metals from contaminated soil. And a soil modifier having a trapping and fixing action.

[0002]

2. Description of the Related Art Crops cultivated in the fields are taken away for sale and are not returned to the soil.
In addition, the overuse of chemical fertilizers that quickly show fertilizer effects reduces humus in the soil or distorts the action of microorganisms in the soil,
It is the cause of the decline of the ground strength. Since ancient times, soil has been made using so-called compost in Japan, and recently, as an organic farming method, cultivation of healthy, safe, and excellent-tasting crops has been widely practiced.
Various materials have come to be used in the production of sapphire.

[0003] On the other hand, in agricultural fields, agricultural chemicals are sprayed, and in non-cultivated lands including green areas, contamination with chemical compounds and their wastes is progressing. Among these pollutants, aromatic halogen compounds are naturally contained. Attention has been paid to those that are difficult to decompose in the environment, and decomposition and removal thereof are desired. In recent years, various attempts have been made to decompose hardly decomposable aromatic halides using microorganisms.

Japanese Patent Application Laid-Open No. 64-68281 discloses a pseudomonas sp KKS102 and a pseudomonas sp.
p KKL101 is mixed with polychlorinated biphenyl (P
It is described that CB) is rapidly decomposed.

Japanese Patent Application Laid-Open No. 8-52454 discloses that a substance containing an organic substance is added to a solid substance such as soil contaminated with an aromatic halogen compound and mixed at 300 to 450 ° C.
And a method of decomposing an aromatic compound by heating, and that a humus, a compost, or the like is used as the organic substance-containing substance.

[0006] Recently, substances that decompose dioxin into wood-rot fungi, a kind of mushroom, have been found one after another. It has been reported that about 90% of dioxins could be degraded by mixing at a concentration of 63 ppm and culturing for 15 days.

[0007]

The composts proposed so far have been satisfactory for the purpose of increasing humus in the soil and growing microorganisms. Further increases are desired.

[0008] On the other hand, the conventional proposals for contaminated soil modification deserve evaluation, in that aromatic halogen compounds such as PCBs and dioxins, which are difficult to decompose, are decomposed and detoxified by the power of microorganisms. However, when applied to actual processing, there are still many problems to be solved.

[0009] That is, the method utilizing microorganisms has the advantage of requiring less energy than the method of decomposing using heat or chemicals, but it is necessary to prepare an environment in which microorganisms can work effectively. In addition, there is a problem that a long time is required for decomposition. In addition, since soil contamination by organohalogen compounds usually occurs over a fairly large area, it is not practical to dig up the contaminated soil and decompose it at another location.

The present inventors have found that the composition of the germicidal bed discharged during mushroom cultivation and the specific siliceous to aluminosilicate activator described below can be used on soil, especially on contaminated soil. To promote the growth of fungi in the soil and to increase humus in the soil by simple means of spraying or further mixing with it, and especially when applied to contaminated soil. Effectively decomposes organic halogen compounds in the soil,
It has also been found that it is effective in capturing heavy metals and the like.

That is, an object of the present invention is to provide a simple means of spraying on the soil and mixing with the soil if desired.
An object of the present invention is to provide a soil modifier capable of promoting the growth of bacteria in soil and increasing humus in the soil, and further improving fertilizer retention, water retention, water permeability and the like. is there. Another object of the present invention is to provide a soil modifier which can decompose and remove contaminants such as organic halogen compounds in contaminated soil and can also capture and fix heavy metals and the like in soil.

[0012]

According to the present invention, (A)
The present invention provides a contaminated soil modifier comprising a disinfecting bed and (B) a siliceous to aluminosilicate activator having a cation exchange capacity of 50 meq / 100 g or more and an ammonia-adsorbing property. In the modifier of the present invention, the siliceous to aluminosilicate activator (B) is used in an amount of 5 to 100 parts by weight, preferably 10 to 100 parts by weight, based on the dry matter (110 ° C.). It is desirable to contain it in an amount of from 70 to 70 parts by weight.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION [Action] In the present invention, a germicidal bed, that is, a germ bed discharged at the time of mushroom cultivation, is selected from wood-rotting fungi-containing materials, and has a specific physical property. It is characterized in that it is combined with a siliceous to aluminosilicate activator.

In the present invention, the germicidal bed is selected from among the wood-rotting fungi-containing materials because the germicidal bed is a material rich in wood-rotting fungi and a large amount of mushrooms are discharged from mushroom cultivation farmers. Because it is easily available. When cultivating mushrooms, the germicidal bed is generated because the same fungus bed can no longer be used to grow mushrooms that are fruiting bodies smoothly. The general view is that growth inhibitory substances have accumulated.

According to the present invention, the combination of a silicic acid or aluminosilicate activator having a specific composition with the germicidal bed promotes the growth of bacteria in the soil and increases humus. In addition, soil such as reclaimed land or reclaimed land can be modified so as to be suitable for organic farming, and the green area can be modified so as to be suitable for growing trees, turfgrass or flowers. Furthermore, by applying this combined soil modifier to soil, it is possible to impart water retention and moderate water permeability, and to improve the retention of fertilizer, thereby promoting the growth of plant stems or leaves. can do.

That is, the reason why the propagation of wood rot fungi on the germicidal bed is suppressed is as described above.
In the present invention, by blending a siliceous or aluminosilicate activator into the evacuation bed, the fungus itself is activated, or a growth inhibitory substance in the evacuation bed is absorbed or adsorbed, or It is considered that the fact that the fungus is activated by decomposing it promotes the growth of the fungus. In addition, it is understood that the biodegradation of the fibrous material, which is the main component of the germicidal bed, effectively progresses due to the growth of fungi, which contributes to the increase of humus in the soil.

The germicidal bed has an odor resembling a peculiar plant odor and is a sticky wet substance.
Although it is a difficult-to-handle waste, by mixing it with a siliceous or aluminosilicate activator, it is possible to deodorize or deodorize odor components in the evacuation bed,
Since this activator absorbs excess water in the germicidal bed, the modifier is always maintained in a smooth state, and has excellent sprayability to contaminated soil and the like.

Furthermore, it is well known that wood rot fungi decomposes contaminants such as organic halogen compounds. According to the present invention, however, the decomposition of organic halogen compounds in soil is promoted. Action is obtained. That is, when the combination of the eradication bed and the siliceous to aluminosilicate activator is applied to the contaminated soil, as compared with the case where the evacuation bed alone is applied to the contaminated soil, the organic halogen compound is clearly obtained. An increase in the decomposition rate is observed.

This decomposition promoting action is not restricted to the present invention in any way for that reason, but is considered as follows. That is, the siliceous to aluminosilicate activator activates the fungus itself, or absorbs or adsorbs the growth inhibitory substance in the evacuation bed, or decomposes it to activate the fungus. And in the degradation cycle of the aromatic halogen compound by fungi, the silicic acid or aluminosilicate activator adsorbs or absorbs the decomposition products or intermediates to shift the equilibrium and promote the decomposition. And so on.

The siliceous to aluminosilicate substance used in the present invention generally needs to have a cation exchange capacity of 50 meq / g or more, particularly 50 to 220 meq / g. When the amount is too small, the soil reforming effect tends to be considerably lower than that in the above range. That is, the cation exchange capacity contributes to the activation of microorganisms and the increase of humus, and also effectively contributes to the improvement of fertilizer retention after being applied to soil.

The siliceous to aluminosilicate activator used in the soil conditioner of the present invention has an ammonia-adsorbing property and an ammonia-adsorbing capacity (static deodorizing capacity) of 3 mg / g or more. Reach the order. Further, the siliceous to aluminosilicate activator used also effectively adsorbs odors other than ammonia. For example, hydrogen sulfide is 88
mg / g, trimethylamine has an adsorption amount of 6.3 mg / g, and ethyl mercaptan has an adsorption amount of 12.1 mg / g. For this reason, when a siliceous or aluminosilicate activator is blended, the odor peculiar to the evacuation bed is effectively deodorized or deodorized, and the handling of the modifier becomes easy. This adsorptivity naturally also contributes to fertilizer retention.

Further, the siliceous to aluminosilicate activator preferably has a water absorption of 15% or more (at 110 ° C. for 90 minutes on a dry basis), particularly preferably a water absorption of 20 to 50%. By using this activator, it becomes easy to enhance the handleability of the contaminated soil modifier, and it is also useful for holding moisture in the soil and supplying water to the roots of plants.

Further, it is preferable that the siliceous to aluminosilicate activator has a soluble silicic acid content of 6 mg / 100 g or more, and this soluble silicic acid content is used for the growth of stems, leaves and trunks of plants. It is also effective in improving soil strength of contaminated soil.

[Bactericidal bed] Bactericidal bed (A) used in the present invention
Refers to used mushrooms used in the cultivation of mushrooms of wood-rotting fungi such as various mushrooms, for example, shimeji mushrooms, enoki mushrooms, oyster mushrooms, nameko or maitake. There are two types of mushroom cultivation: raw wood cultivation, in which fungi are planted on logs to grow mushrooms, and fungal bed cultivation, which grows them on fungal beds made of sawdust, etc., but cultivation in a short period of time is possible. In addition, fungus bed cultivation is advantageous in that the yield per space is large, and is widely used for actual mushroom cultivation. In the present invention, the germicidal bed discharged during the cultivation of the mushroom is effectively used for producing a contaminated soil modifier. This bed has almost pure form of wood-rot fungi.
In other words, it is contained in a form substantially free of various germs, and this is useful for modifying contaminated soil in combination with a siliceous or aluminosilicate activator.

As the fungal bed, a medium obtained by mixing a nutrient source, an inoculum or a nutrient into a medium (culture medium) mainly composed of plant fiber is used. As a vegetable medium (culture medium), sawdust, pagasu, corn cob (a corn core crushed product), rice husk, and the like are used alone or in combination of two or more. As sawdust, hardwood or softwood sawdust, particularly hardwood sawdust, is particularly suitable.
As a nutrient source, rice bran, bran, soybean hull, barley bran, corn, powdered sugar, waste bee sugar, pomace of beans and the like are used alone or in combination of two or more.

The above-mentioned bacterial bed components are sterilized so as not to be mixed with various bacteria, and are mixed with the above-mentioned species of wood-rotting fungi. The mixing ratio varies depending on the type and culture conditions of the mushroom, but generally speaking, per 100 parts by weight of the plant medium,
Nutrition source is 96 to 98.5 parts by weight, bacterial species is 0.1 to 1
It is desirable that the nutritional supplement be in the range of 1.4 to 3 parts by weight.

In cultivation of mushrooms, the above components are kneaded with water, filled into a plastic bottle or a bag, and cultured (ripening from the generation of hyphae), sprouting (formation of a bulk body of the fruiting body from generation of fruiting body), Perform processing such as fruiting body growth. Each of these processes is performed under known optimum conditions according to the type of each mushroom. The above culture is generally performed in 2
At a temperature of 0-25 ° C. and humidity of 70-80% RH,
It is performed for about 90 to 100 days in a dark place. The above germination is generally carried out at a temperature of 20 to 25 ° C. and 70 to 80%
It is preferable to carry out in a dark place at a humidity of RH for about 70 to 80 days. The growth of the fruiting body is generally performed at a temperature of 20 to 25 ° C. and a humidity of 70 to 80% RH in a bright place for about 10 to 30 days.

After mushrooms grow and are harvested,
By repeating the same operation, mushrooms can be harvested two or three times, and the harvested bacterial bed is effectively used as a component of the contaminated soil modifier of the present invention.

[Silica to aluminosilicate activator] In the present invention, 5 as an essential component of the contaminated soil modifier is used.
A siliceous to aluminosilicate activator having a cation exchange capacity of 0 meq / g and ammonia adsorption is used.

The silicic or aluminosilicate activator (B) can be used without any particular limitation as long as it has the above-mentioned properties and chemical composition. In a preferred order, the powdery granules of the filter cake (silica-alumina) produced when the acidic waste liquid discharged in the acid treatment step of clay and the alkaline waste liquid and / or lime discharged in the synthesis step of zeolite are mixed and neutralized are mixed. Composite powder), waste clay used for the purification of fats and oils or its treated products, activated bentonite used as pet toilet sand, aluminum-containing zinc phyllosilicate or its amorphous silica composite, etc. Can be mentioned. Of course, these can be used alone or in combination of two or more. The typical examples of the siliceous to aluminosilicate activator (B) will be described in detail below, but the chemical structure and physical properties will be described.

(1) Silica-alumina composite powder The acidic waste liquid produced in the clay acid treatment step contains a basic component contained in the clay, ie, an alumina component, an alkaline earth metal component, an iron component, etc., in water. The silica component is contained in the form of an acidic sol while being contained in the form of an acidic salt. On the other hand, the alkaline waste liquid discharged in the zeolite synthesis process includes alkali aluminate, alkaline sol of silica,
Further, it contains fine particles of amorphous or crystalline zeolite. Thus, when the acidic waste liquid is neutralized with lime or the alkaline waste liquid, amorphous silica, amorphous alumina, amorphous or crystalline silica alumina or aluminosilicate (including zeolite), iron hydroxide Precipitate as a precipitate in the state where the material or oxide, gypsum, etc. are composited,
Most of these components are components having excellent adsorptivity such as cation exchange ability and hygroscopicity, and are substantially composed of components which are insoluble or hardly soluble in water.

In addition, silicate and / or alumina
Although the primary particles are extremely fine,
Particles form a porous structure that aggregates with each other or with other components
And a structure having a high coarse porosity. example
For example, the unit volume weight according to JIS A 1104
In the natural state, for example, 1.479 g / cm in the case of mountain sand
³In contrast, the above silica-alumina composite powder
0.85 to 0.99 g / cm³Within the range of
It is porous. Therefore, this silica-alumina composite powder
The body is excellent in water retention, and in the natural state, JSF
 The moisture content by the T121 method is also 10.9% in the case of mountain sand.
Is in the range of 80 to 180%.

Further, the silica-alumina composite powder is
It is a component contained in soil and the like, does not contain any harmful components, and is finally reduced to soil, and is excellent in safety. In addition, the silica-alumina composite powder has a component that is originally excellent in adsorptivity, and the inside of the granular material is porous, has excellent water retention, and has excellent handling properties of the soil modifier. When applied as a soil modifying agent, it has the effect of preventing drying of soil and roots. Furthermore, as is apparent from the unit volume weight, derived from the porous structure, it has excellent water permeability and air permeability, is easy on roots, and has no stagnation of rainwater, etc., and has a large true specific gravity. It does not flow out even in heavy rain, and it is not blown off by the wind,
Excellent wind resistance. Furthermore, because it is an inorganic substance,
It is not ignited by cigarette fire or the like, and is excellent in flame retardancy. Moreover, since it is a synthetic inorganic component, it has a property that it is difficult for weeds to grow, that is, it is excellent in weed control. In addition, since the silica-alumina composite powder is composed of a water-insoluble component and has a solid coagulated structure, the granulated material has an advantage that the granular structure is maintained without weathering for at least about three years. . Furthermore, it has a good particle size, so that it is excellent in workability such as transportation and application, and because it is a product recovered from waste liquid, it is low in cost and excellent in economic efficiency.

The silica-alumina composite powder has a pale yellowish brown appearance substantially similar to that of earth material, and is derived from clay, which is a natural mineral, and contains no harmful substances. It also has the advantage that the natural feeling of the soil is not spoiled and the natural environment is not spoiled.

The silica-alumina composite powder used in the present invention is produced when the acidic waste liquid discharged in the clay acid treatment step and the alkaline waste liquid and / or lime discharged in the zeolite synthesis step are mixed and neutralized. It is obtained by granulating the filter cake into certain granules.

As the raw material clay, smectite clay,
Particularly, montmorillonite such as acid clay or bentonite is used, and halloysite is also used. It is considered that smectite was generated by the denaturation of volcanic ash and lava under the influence of seawater.

The above smectite clay mineral is subjected to purification operations such as stone and sand separation, buoyancy separation, magnetic separation, elutriation and elutriation if necessary, and then to acid treatment. The purpose of the acid treatment of these clays is to obtain activated clay, a color developing agent for pressure-sensitive paper, amorphous silica, etc. useful as a fat refining agent or a catalyst carrier. In this treatment, acidic waste liquid is produced as a by-product. Is what you do.

The acid is an acid such that a salt of a metal in a clay mineral and an acid radical of the acid used is soluble in water or an aqueous acid solution, and mineral acids such as sulfuric acid and hydrochloric acid and organic acids are also used. However, mineral acids, especially sulfuric acid, are advantageously used in terms of economy and handling. It is advantageous from the point of the acid treatment operation that the concentration of the acid used is generally in the range of 5 to 50% by weight, especially 15 to 35% by weight. The temperature of the acid treatment is generally in the range of 50 to 100 ° C., preferably 60 to 95 ° C.,
The acid treatment time is selected from 1 to 30 hours, particularly 5 to 25 hours, and a combination of temperature and time is selected according to the type of the raw material mineral and the acid concentration so as to satisfy the above-mentioned conditions. The contact between the raw material mineral and the acid is carried out by granulating the raw material mineral into certain granules, filling the granulated material in a tower and circulating the acid aqueous solution in the tower, or dispersing the raw mineral in the acid aqueous solution. Let
It is performed by a method of performing an acid treatment in a slurry state or the like.

By this acid treatment, cations between layers contained in the raw material mineral elute as a salt into the aqueous acid solution, and
Metal components such as the Mg component, the Fe component, and the Al component in the octahedral layer having a layer structure and the Al component in the tetrahedral layer having a three-layer structure are eluted as salts into the aqueous acid solution. Further, a part of the silica component in the clay is eluted in the form of an acidic sol. At the end of the acid treatment, the acid aqueous solution containing these salts is separated from the acid-treated smectite clay. In addition, a washing solution of the acid-treated product may be used for the same neutralization treatment.

The acidic waste liquid is mixed with an alkaline waste liquid and / or lime discharged in a zeolite synthesis step, neutralized, and the silica component and the metal component contained in the acidic waste liquid are recovered as a precipitate. This neutralization reaction is carried out when the pH of the solution is 6.
To 9, especially 7 to 8. The temperature of the neutralization reaction is suitably in the range of 20 to 90 ° C.

The alkaline waste liquid and lime discharged in the zeolite synthesis step may be used alone for neutralization or may be used for neutralization in combination. For example,
The alkaline waste liquid discharged in the zeolite synthesis process may be used in the initial stage of neutralization, and lime may be used in the final stage of neutralization. The lime may be added to the acidic waste liquor in solid form or may be added to the acidic waste liquor in the form of lime milk.

As the alkaline waste liquid discharged in the step of synthesizing the zeolite, an alkaline waste liquid produced as a by-product in the synthesis process of all crystalline or amorphous synthetic zeolites is used. In the synthesis of zeolites, sodium silicate, sodium aluminate and sodium hydroxide, or even activated silicic acid, depending on the desired zeolite,
Na ₂ O / SiO ₂ , SiO ₂ / Al ₂ O ₃ and H ₂ O
/ Na ₂ O is mixed so that the molar ratio is within a certain range to form a gel of alkali aluminosilicate. After homogenizing the gel, the gel is heated at a temperature of 80 to 200 ° C. under normal pressure or hydrothermal conditions. By reacting, zeolite is synthesized. The generated zeolite is separated from the alkaline waste liquid,
The alkaline waste liquid washed and separated is used for neutralizing the acidic waste liquid. The above-mentioned components are contained in this alkaline waste liquid, and these components are recovered during precipitation.

The precipitate to be purified by the neutralization is separated from the waste water by a filter such as a filter press into a solid and a liquid, and the obtained filter cake is granulated as it is, unless otherwise required. Granules are generally from 5 to 50 mm, especially from 10 to 3 mm.
It is desirable to have a particle diameter of 0 mm, and a granulation method such as a crushing granulation method, an extrusion granulation method, a tablet granulation method, a rolling granulation method, or the like is used. Of course, granulation may be performed after washing and drying the filter cake as necessary. If a raster filter manufactured by Ishigaki Kiko Co., Ltd. is used at the time of filtration, the water content of the filter cake can be dehydrated to 65% or less, particularly 50% or less.

The silica-alumina composite powder used in the present invention contains alunite, gypsum, zeolite and amorphous silicate as essential components. FIG. 1 of the accompanying drawings is an X-ray diffraction image of the silica-alumina composite powder, confirming the presence of alunite, gypsum, and zeolite as crystalline components. Alunite is represented by the following formula (1): MAl ₃ (SO ₄ ) ₂ (OH) ₆ (1) wherein M is an alkali metal, and the basicity of aluminum and alkali metal represented by the formula It is a sulfate mineral, insoluble in water, but has cation exchange properties. Gypsum exists in the form of crystalline gypsum, i.e., dihydrate. Zeolites are tectoaluminosilicates and also contribute to cation exchange and adsorption. The zeolite so-called A-type zeolite, i.e., the following formula _{(2) Na} 2 typically present as zeolite composition represented by _{O · Al 2 O 3 · 2SiO} 2 · nH 2 O ···· (2) It is. Amorphous silicate is, of course, not detected on X-ray diffraction, but its presence is confirmed by chemical analysis. The amorphous silicate not only helps to form a porous structure, but also improves the adsorptivity.

The silica-alumina composite powder was heated at 45 ° C.
On a dry basis for 24 hours, generally SiO ₂ 15 to 4
5% by weight, 15 to 30% by weight of Al ₂ O ₃ , Fe ₂ O
₃ 1 to 15% by weight, CaO 5 to 20% by weight, SO
₄ 10 to 30% by weight and loss on burning (1050 ° C) 1
It has a chemical composition of 0 to 30% by weight.

Further, this silica-alumina composite powder is
It is preferable to have a pH of 6 to 9 as measured as an aqueous suspension in order to prevent damage by acids and alkalis. Further, the silica-alumina composite powder has a cation exchange capacity (CEC) in the range of 50 to 220 meq / 100 g. The value of CEC is about 4 to 10 times that of natural mountain soil and mountain sand, and is excellent in so-called fertilizer retention and retention. This is because this powder is
It belongs to containing ion exchange components such as zeolite (sodium aluminosilicate).

(2) Waste Clay and Its Treated Product Waste clay used as the component (C) of the composition of the present invention is used as decolorizing or refining clay for decolorizing or refining oils and fats, and is separated as a by-product in this step. It contains oil,
It is not permissible to discard this from the viewpoint of environmental pollution, and its effective use has been eagerly desired.

That is, a montmorillonite family clay mineral such as acid clay, or activated clay obtained by treating these clay minerals with an acid and / or an alkali is added to the fat or oil to be decolorized or refined in the form of a powder. The coloring component and the impurity component contained in the fats and oils are adsorbed on the clay particles by adding them as a refining agent and stirring them uniformly.
In the clay separated after the decolorization or purification treatment, an amount of fats and oils corresponding to the oil absorption of the used clay is retained.

The decolorizing treatment of fats and oils is a condition known per se, for example, 0.1 to 5% by weight of clay per fat or fat is added as a decolorizing or purifying agent, and 90 to 150 ° C.
By stirring the two compositions at a temperature of 5 to 30 minutes, the decolorization or purification treatment can be completed.

The mixture after the decolorization or purification treatment is supplied to an optional filter, for example, a reduced or pressurized filter such as a filter press, a belt filter, an Oliver filter, an American filter, or a centrifugal filter. A so-called waste clay, which is a refined oil or fat and a used decolorizing or refining agent, is obtained. Although depending on the type of raw material oil to be refined, this waste clay generally contains a small amount of oil which is retained by particles and cannot be separated, in an amount of about 25 to 35% by weight.

The clay used as a decolorizing agent or a purifying agent is
It is a montmorillonite group clay mineral such as acid clay and its chemically treated product.

The montmorillonite family clay minerals such as acid clay have a basic unit of a three-layer structure in which two SiO ₄ tetrahedral layers are sandwiched with an AlO ₆ octahedral layer interposed therebetween. This is an aluminosilicate in which a layer structure is further laminated in the C-axis direction to form a layered crystal structure. This layered crystal structure is common to montmorillonite group clay minerals.

Among the montmorillonite, acid clay widely produced in Japan is, due to weathering, an AO ₆ octahedral layer in a three-layer structure which is a basic unit of montmorillonite.
A part of the l atom is replaced by an alkaline earth metal such as magnesium or calcium, and a hydrogen ion is bonded to make up the valence. Therefore, when the acid clay is suspended in a saline solution and its pH is measured, the hydrogen ions are replaced with sodium (Na) ions, indicating that the clay is acidic.
On the other hand, bentonite has a pH ranging from neutral to slightly alkaline and has a large water swelling property because the exchangeable cation is mostly sodium (Na), whereas sodium ion is an alkaline earth metal in acid clay. Since it is substituted, the alkali metal component is small, the water swelling property is low, and the content of silicic acid is high, it is extremely advantageous in terms of adsorptivity. Thus, as the montmorillonite, any acid clay produced in Japan is widely used, and a montmorillonite group clay mineral called so-called sub-bentonite (Ca-type bentonite) is also used.

An X-ray diffraction pattern of a representative acid clay is shown in FIG. 2 (see Examples). Table 1 below shows the acid clay (100 ° C
An example of the general chemical composition of the dried product is shown below.

[0055]

TABLE 1 SiO ₂ 61.0 ~ 74.0 _{(wt%) Al 2 O 3 12.0 ~} 23.0 Fe 2 O 3 2.0 ~ 3.5 MgO 3.0 ~ 7.0 CaO 1.0 ~ 4.0 K 2 O 0.3 ~ 2.0 Na 2 O 0.3 ~ 2.0 Ig-loss 5.0 to 10.0

When using acid clay, the rocks contained therein, such as cristobalite, quartz, feldspar, etc., can be easily separated by a separation method utilizing a specific gravity difference (classification means such as elutriation or elutriation). Can be. In addition, cristobalite, a crystalline silicic acid, can easily react with an alkali to be converted into an alkali silicate, and thus can be removed by this method. By these methods, the purity of the layered crystal structure can be improved.

On the other hand, acid-treated clay is generally known as activated clay, which is a refining agent for oils and fats. This acid-treated product is easily prepared by treating an acid clay with a mineral acid solution such as sulfuric acid or hydrochloric acid to elute a part of the basic components contained therein and washing the same. This acid treatment destroys a part of the layered crystal structure originally possessed by the acid clay, but increases the content of silicic acid (SiO ₂ ), thereby increasing the specific surface area and the adsorbing capacity. Physical properties are improved. An acid-treated clay, an activated clay generally available on the market, and a waste clay obtained by using an intermediate product thereof are treated with excellent properties.

The chemical composition of this acid-treated product varies depending on the type of the raw acid clay, the acid treatment conditions, and the like, but generally has the composition shown in Table 2 below.

[0059]

Table 2 SiO ₂ 65.0 to 83.0 (% by weight) Al ₂ O ₃ 5.0 to 12.0 Fe ₂ O ₃ 1.0 to 3.5 MgO 1.0 to 7.0 CaO 0.5 to 4.0 K ₂ O 0.2 to 2.0 Na ₂ O 0.2 to 2.0 Ig-loss 5.0 to 10.0

The raw material fats and oils are widely present in the natural animal and plant kingdoms and are mainly composed of esters of fatty acids and glycerin. For example, safflower oil, soybean oil, rapeseed oil, palm oil, palm kernel oil, Sunflower oil, Beni flower oil, sesame oil, cottonseed oil, olive oil, coconut oil, corn oil, rice bran oil, tung oil,
Vegetable oils such as peanut oil, castor oil, linseed oil, camellia oil, kapok oil, cacao oil, wax, etc., and fish oils such as sardine oil, herring oil, squid oil, saury fish oil, liver oil, whale oil, tallow oil, beef tallow oil, Animal oils and fats such as horse oil, lard and sheep fat alone or in combination.

The above-mentioned waste clay is made of aluminosilicate having excellent adsorption characteristics, and at least a part, preferably most of oil contained in pores and the like in the waste clay is preferably plant-based. It is also used as a nutrient for fungi as well as a component of fertilizer, so it is restored to have a large cation exchange capacity, specific surface area and pore volume, and this property is useful for enhancing the ground force.

Of course, it is desirable to avoid use in a form in which an excessive amount of oil remains in the soil conditioner, because this is because of the waste clay in the siliceous to aluminosilicate activator (B). This can be achieved by adjusting the amount or adjusting the oil content in the waste clay. In the former case, that is, when the oil-containing waste clay is used as it is, the amount of waste clay used is preferably 5% by weight or less, more preferably 3% by weight or less per silicic or aluminosilicate activator (B). . In the latter case, the oil-impregnated waste clay is subjected to a steaming process to recover as much of the oil content of the waste clay as possible, and the oil-impregnated waste clay is subjected to a heat treatment to reduce the oil content of the waste clay. A part obtained by carbonizing the part and carbonizing the remaining part is advantageously used.

As an example, a heat-treated product of waste clay is a dry base.
7 to 30% by weight, especially 10 to 30% by weight of charcoal
Element, 54 to 75% by weight, especially 60 to 70% by weight of S
iO ₂And 6 to 12% by weight, especially 8 to 11% by weight
Al₂O₃Containing, 20 to 200 m²/ G, especially
50-200m²/ G BET specific surface area and 0.05
0.3cm³/ G, especially 0.1-0.3cm³/ G
Having a pore volume of

The specific surface area and pore volume of raw clay used for refining oils and fats are generally from 200 to 300 m ² / g and from 0.1 to 0.2 m ² / g.
The range of ^{3 to} 0.4 cm ³ / g reveals the fact that this heat-treated product achieves a regeneration rate of about 80%.

The silica and alumina having the above-mentioned ratios contained in the treated material can serve as excellent adsorption sites for various components, and the carbon contained in the treated material can also be adsorbed. It is thought to contribute to sex.
For example, as shown in an example to be described later, this treated product has a strong adsorption performance for malodorous components such as ammonia and hydrogen sulfide, and also has a function as a deodorant having a wide deodorizing spectrum.

(3) Used pet toilet sand Silicic to aluminosilicate activator (B)
Granules of natural bentonite or activated bentonite used as pet toilet sand can be used.
The granules are preferably between 80 and 800 m ² / g
Has a BET specific surface area of 0.2 to 2.3 ml / g, and absorbs urine of pets such as cats to facilitate removal of only wet parts. It has a function of solidifying and adsorbing malodors caused by human waste. In the present invention, those used for this purpose and discarded are used.

The granular bentonite is generally 1 to 1
It preferably has a particle size of 0 mm, especially 2 to 5 mm. The particle shape may be any shape such as a sphere, a cube, a column, a prism, a granule, a tablet, and an irregular shape.

Suitable bentonite is disclosed in Japanese Patent Publication No. 5-736.
No. 89, which is composed of activated bentonite, which contains montmorillonite as a main component and cristobalite as a small component, and is expressed by a molar ratio: AlO ₂ / SiO ₂ = 0.095 to 0 .16 Na ₂ O / SiO ₂ = 0.8 × 10 ^{−2 to} 4.5 × 10 ⁻² MO / SiO ₂ = 4.5 × 10 ^{−2 to} 9.5 × 10 ⁻² (where M is has a chemical composition of an alkaline earth metal), in ACC method degree of swelling 30 cm ^3/2 g or more, and flow behavior index (n) is of 0.53 or less.

(ACC method swelling degree) ion-exchanged water 100c
m ³ in a 100 cm ³ graduated cylinder with a stopper
2 g of a sample (with a water content of 4 to 10.0%) is added so as to hardly adhere to the inner wall. After most of the previously added sample has settled, the next sample is added. When the addition is completed, stopper the sample and allow it to stand for 24 hours, and read the apparent volume of the sample deposited in the container. To display the unit of swelling power as ^(cm 3 / 2g).

(Flow Behavior Index) The flow behavior index (n) is
The following equation (3) In the formula, it is θ _r distilled water 350cc in bentonite 22.5
Shear stress (lb / 100 ft ² ) measured using a fan VG rotational viscometer under the condition of 300 g / g at a speed of 300 rpm.
And θ _2r is a shear stress (lb / 100f) measured in the same manner as described above except that the number of rotations is set to 600 rotations / minute.
t ²⁾ represents, G ₀ gel stress, i.e. 600 rev / min was rotated for 10 seconds, stopping the rotation to the 3 rev / min after standing for 10 seconds rotating shear stress is measured as described above ( lb / 100 ft ² ).

The pet urine contained in the used pet litter is also a fertilizer for plants and also a nutrient for fungi.
The cation-adsorbing property, the water-absorbing action, and the adsorptive action peculiar to bentonite are exhibited, and the soil force enhancing action on soil is effectively performed.

(4) Zinc-containing aluminum phyllosilicate or amorphous silica composite thereof The zinc-containing aluminum phyllosilicate used as at least a part of the activator in the present invention comprises a tetrahedral layer of silica or silica-alumina. , And an octahedral layer of ZnO ₆ —AlO _{6 in} a two-layered basic skeleton, and has a structure in which this basic skeleton is laminated in the C-axis direction.

A typical aluminum-containing zinc phyllosilicate is represented by the following formula (4): (Zn _3-x Al _x ) (Si _2-x Al) O ₅ (OH) (4) Has a chemical structure represented by being a number from 0.1 to 1.75 and is referred to as frypontite. That X
FIG. 3 shows a line diffraction image.

The aluminum-containing zinc phyllosilicate is obtained by mixing a raw material for silicic acid such as diatomaceous earth and cristobalite, a zinc raw material such as zinc oxide, and an alumina component such as boehmite gel in an aqueous solution of a water-soluble salt such as ammonium chloride. In addition,
It is manufactured by performing a hydrothermal synthesis reaction at 110 to 300 ° C. in an autoclave container.

Details of the structure, physical properties and production method of the fly-pontite type zinc-containing aluminum fluorosilicate are described in JP-A-61-10021, 61-275128 and 61-275128.
-275127.

In the present invention, it is particularly preferable to use a siliceous composite of aluminum-containing zinc phyllosilicate. More specifically, the composite comprises amorphous porous silica or silica-alumina and an aluminum-containing phyllosilicate layer formed on the surface of the primary particles.

The chemical composition is 5 to 80 mol% of SiO _2, 5 to 65 mol% of ZnO, and 1 to 60 mol% of Al ₂ O _{3 in} a three-component composition ratio as a whole.

The siliceous composite had substantially no peak at a plane spacing (dX) of 8.40 to 6.40 angstroms by X-ray diffraction, and a plane spacing (dX) of 2.71 to
2.56 angstroms and spacing (dX) 1.56
It has a peak at 1.52 Å, a specific surface area of 200 m ² / g or more, and a pore volume of 0.25 cm ³ / g or more at a pore diameter of 10 to 300 Å.

In the above composite, amorphous porous silica or silica alumina is preferably present in an amount of 10 to 70% by weight based on the whole. In other words, below this range, the effect of miniaturizing the aluminum-containing zinc phyllosilicate is lost, and above this range, the adsorptivity becomes inferior to those within the above range.

The composite phyllosilicate is obtained by adding a water-soluble silicate, a water-soluble zinc salt, and a water-soluble aluminum salt and / or aluminate to an aqueous medium containing a sol or gel dispersion of silica or silica-alumina. The total composition of the three components is SiO ₂ 5 to 80 mol%, ZnO 5
To 65 mol% and 1 to 60 mol% of Al ₂ O _3, and reacting the added salts in the presence of silica or silica alumina.

At the time of the synthesis, the sol or gel dispersion of silica or silica alumina was dried in an amount of 200 m ² /
g or more,
The silica-alumina sol or gel dispersion may contain up to 80% by weight of Al ₂ O ₃ .

The sol-gel dispersion of silica or silica-alumina is used in an amount of 10 to 70% by weight per composite phyllosilicate.
And the solid content of silica or silica-alumina in the aqueous medium is preferably 1 to 20% by weight. Further, the reaction is preferably carried out at a temperature from room temperature to 100 ° C. and a pH of 5 to 10.

In the above aluminum-containing zinc phyllosilicate and its complex, it is preferable that all of the divalent metals are zinc alone.
It is permissible to include them in an atomic ratio of 5 to 50:50.

In the present invention, when an aluminum-containing zinc phyllosilicate or a siliceous complex thereof is used as at least a part of the activator, it is particularly excellent in deodorizing effect, not only ammonia odor but also hydrogen sulfide and the like. Excellent deodorizing effect is obtained for mercaptans and thioethers. The aluminum-containing zinc phyllosilicate or the siliceous complex thereof is used for a deodorant or an adsorbent, but it is of course possible to use a discarded one after use, as an activator. This aspect is desirable in terms of cost reduction.

[Soil conditioner and its production] The soil conditioner according to the present invention is based on a dry matter (110 ° C) based on the bactericidal bed (A).
5 to 100 parts by weight, especially 10 to 70 parts by weight of the siliceous to aluminosilicate activator (B) per 100 parts by weight
It is preferable to contain it in an amount of part by weight.

When the amount of the siliceous to aluminosilicate activator (B) is less than the above range, the activation of wood rot fungi on the evacuation bed is inferior to the case where the amount is within the above range. In addition, it takes a long time to modify the soil, and the handling property of the soil modifying agent also decreases. In addition, the decomposition effect on contaminants such as organic halogen compounds tends to decrease. On the other hand, when the amount of the siliceous to aluminosilicate activator (B) exceeds the above range, the amount of the inorganic component in the soil modifying agent becomes too large, so that the growth of microorganisms is promoted and the amount of humus is increased. Tends to be difficult to increase.

The soil conditioner of the present invention contains the above two components as indispensable components. The soil conditioner includes a conventionally known soil conditioner or a soil conditioner. Can be blended. For example, green manure crops, crop residues, carbonized materials (charcoal, rice charcoal), park compost, straw / deciduous compost, peat, humic acid materials, shell fossil powder, diatomaceous earth fired granules, city garbage compost, livestock poultry manure Animal and plant materials such as fertilizer and crab shell powder; mineral materials such as vermiculite, perlite and slag; polymer compounds such as polyvinyl alcohol and polyethyleneimine; fertilizers such as calcareous fertilizer and phosphate fertilizer; One or a combination of two or more can be used as the auxiliary material. These secondary materials are preferably used in an amount of 50 parts by weight or less, particularly 30 parts by weight or less, per 100 parts by weight of the evacuation bed.

The soil conditioner of the present invention is produced by mixing the above-mentioned components and forming the mixture into a powder. Mixing can be performed using any mixer known per se, for example, a stirring or kneading mixer.
Generally, a screw-type mixer having a single-screw or multi-screw is advantageously used, in which the raw material is charged from one end (feed hopper) and the mixture is formed into a granular form from the other end (extrusion port). Take out with.

The resulting mixture can be used as it is as a soil modifier in the form of a granular material. However, in general, it is generally used after aging once to activate fungi and then use as a soil modifier. Good. Aging is generally preferably performed at a temperature of 60 to 80 ° C. for about 10 to 30 days. Aging is performed using an aging tank. The aging tank may be a fixed bed type or a moving bed type, but by using a moving bed type aging tank using a conveyor or the like, processing can be performed efficiently.

Further, a photocatalyst (photoreactive semiconductor), for example,
The performance is further improved by blending titanium oxide, tungsten oxide, zinc oxide, cerium oxide, strontium titanate, potassium niobate, and the like.

The thus prepared soil modifying agent can be used for spraying the soil as it is, but it is desirable to granulate it into a granular material which can be easily handled. The granulation operation can be performed using any known granulator, extrusion granulator, crushing granulator, tumbling granulator, compression granulator, tableting machine and the like. The shape of the object may be any shape such as a spherical shape, a rugby ball tablet, a columnar shape, a prismatic shape, and an irregular shape. The size of the granular material is not particularly limited, but is generally in the range of 5 to 50 mm in terms of handling. Granulation of the soil modifying agent can be advantageously performed using a rotary granulator having holes in the cylinder wall. According to this granulation operation, the rolling granulation by the cylinder wall surface and the classification of the fine particles through the holes are simultaneously and efficiently performed, which is convenient. The separated fine particles can be circulated to a mixer and reused.

The soil modifying agent of the present invention is effective for modifying soil in fields, orchards, horticulture, various nurseries, green areas, etc.
It promotes soil agglomeration, aids the growth of micro-organisms, increases humus, and aids in the strengthening of soils with reduced strength. In addition, the fertilizer after fertilization is good, the root growth, foliage growth, tillering are active, and a wide range of crops such as strawberry, tomato, cucumber, cabbage, Chinese cabbage, spinach,
It can be applied to cultivation of ginseng, leeks, peppers, peas, watermelons, pears, grapes, peaches, apples and the like, as well as trees, turfgrass, flowers and the like. In particular, cultivation on land contaminated with agricultural chemicals and industrial waste, and greening of road fills and cut-offs contaminated with the combustion waste of leaded gasoline not only helps to strengthen the soil's soil strength, It also has the advantage of being useful for decomposing organic halogen compounds or for adsorbing and fixing lead components. The soil conditioner of the present invention varies significantly depending on the degree to which the condition is required to be modified, but is generally 200 to 50 per unit area (1 m ² ) of the soil.
It is good to spray about 0 g and mix with soil by excavating if necessary.

[0093]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to the following examples. In addition, the measuring method in an Example is as follows.

(1) X-ray diffraction Using a RAD-IB system manufactured by Rigaku Denki,
It was measured by u-Kα. Target Cu filter Curved crystal graphite monochromator Detector SC voltage 40 kVP Current 20 mA Count full scale 700 c / s Smoothing point 25 Scanning speed 1 ° / min Step sampling 0.02 ° Slit DS1 ° RS0.15mm SS1 ° Illumination angle 6 °

(2) Chemical composition For the ignition loss (Ig-loss), the sample treated at 45 ° C. for 24 hours was heated to 1050 ° C., and the decrease was measured. Silicon dioxide (SiO ₂ ), aluminum oxide (A
l ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ), calcium oxide (CaO), and magnesium oxide (MgO) were analyzed by JI
S. M. It was measured according to 8855.

(3) Cation exchange amount (CEC) The cation exchange amount was expressed in meq / 100 g according to the test method TIKS-413 issued by the Japan Foundry Association, Inorganic Sand Mold Research Group, Tokai Branch.

(4) Soluble Silicic Acid Content A 1 g sample of a dried product at 45 ° C. was weighed at 150 ° C. for 30 minutes at 150 ° C. for 30 minutes.
The mixture was shaken for 1 hour (30 to 40 rpm), cooled quickly, made up to 250 ml with water, filtered, and a fixed amount of the solution was quantified by a perchloric acid method to obtain a soluble silicic acid content.

[Shimeji cultivation method] 1 Kg of shimeji strain, 1200 Kg of corn bump, 390 Kg of bean husk, nutritional supplement 1
After thoroughly mixing 05 Kg, 260 kg of powdered sugar and 3200 cm ³ of water, the mixture is bottled. Then, in a dark room at a temperature of 20 ° C,
It was left at a humidity of 70% for 75 days and aged for 20 days to grow shimeji. After the cultivation, the grown shimeji is harvested, and the remaining bacterial bed is collected.

(Synthesis of aluminosilicate activator) To the acidic waste liquid discharged in the sulfuric acid treatment step of the acid clay, the alkaline waste liquid discharged in the synthesis step of A-type zeolite and the slaked lime solution prepared in advance are added and mixed. Neutralized to obtain a filter cake. This filter cake was granulated while drying the surface with a rotary kiln and passed through a sieve to obtain an aluminosilicate activator having a diameter of 10 to 30 mm. Table 3 shows the composition of Sample 1 and FIG. 1 shows an X-ray analysis chart.

[0100]

[Table 3]Chemical composition (%) SiO₂22.0 Al₂O₃ 21.0 Fe₂O₃ 3.3 CaO 10.0 MgO 3.6 SO₄ ^2- 10.9Cl ⁻ 0.4  CEC (meq / 100g) 87.9 Soluble silicic acid content (mg / 100g) 8

Example 1 1200 Kg of evacuation bed (360 Kg based on dry matter (110 ° C.)) and 120 Kg of aluminosilicate activator (72 Kg based on dry matter (110 ° C.))
g) in a kneader (20 parts by weight of the aluminosilicate activator when the bacteria-free bed is 100 parts by weight based on dry matter (110 ° C.)), and aged at 60 ° C. for 25 days.
A soil modifier was obtained. Using the obtained soil modifying agent, the soil of a certain land was modified. In order to see if the soil was improved, a test was conducted to grow Komatsuna. Komatsuna seeds were planted in unmodified soil and in soil after modification, respectively, and the germination (seed germination rate) and growing condition (elongation of buds) were examined.
Table 4 shows the results of the growth.

[0102]

[Table 4] Germination Growth status (cm) Day 2 Day 5 Day 10 Day 15 After soil modification Good 1 4 12 17 Before soil modification Bad 0 1 3 6

[0103]

According to the present invention, (A) the evacuation bed and (B)
A siliceous or aluminosilicate activator having a cation exchange capacity of 50 meq / 100 g or more and an ammonia adsorbing property is combined and used as a soil modifier, so that it is dispersed on the soil and, if desired, this soil is dispersed. With the simple means of mixing with water, the growth of bacteria in the soil can be promoted, the humus in the soil can be increased, and the fertilizer retention, water retention, water permeability, and the like can be further improved. Further, when applied to contaminated soil, contaminants such as organic halogen compounds in soil can be decomposed and removed, and heavy metals and the like in soil can be captured and fixed.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction image of a silica-alumina composite powder.

FIG. 2 is an X-ray diffraction image of acid clay.

FIG. 3 is an X-ray diffraction image of aluminum-containing zinc phyllosilicate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) C09K 17/12 B09B 3/00 304K 17/32 (72) Inventor Hideyuki Sato Nihonbashi Muromachi 4 Chuo-ku, Tokyo No. 1-21 Mizusawa Chemical Industry Co., Ltd. F term (reference) 2B022 AB20 BA01 BA02 BA04 BB01 DA19 2E191 BA12 BB01 BC01 BC05 BD20 4D004 AA41 AB06 AB07 AC07 CA18 CA34 CA47 4H026 AA02 AA10 AB04

Claims (9)

[Claims] (A) a bacteria-free bed and (B) 50 meq / 1.
A soil modifier comprising a siliceous to aluminosilicate activator having a cation exchange capacity of at least 00 g and an ammonia adsorbing property. 2. The method according to claim 1, wherein the silicic acid to aluminosilicate activator (B) is contained in an amount of 5 to 100 parts by weight per 100 parts by weight of the germicidal bed (A) on a dry matter (110 ° C.) basis. 2. The soil modifier according to 1. 3. The germicidal bed (A) is a shimeji, enoki mushroom,
The soil modifying agent according to claim 1 or 2, which is an exclusion bed of oyster mushroom, nameko, or maitake. 4. The water absorption of the silicic acid to aluminosilicate activator is 15% or more (at 110 ° C. for 90 minutes on a dry basis).
The soil modifier according to any one of claims 1 to 3, which has: 5. The soil conditioner according to claim 1, wherein the siliceous to aluminosilicate activator has a soluble silicic acid content of 6 mg / 100 g or more. 6. An acidic waste liquid discharged in a clay acid treatment step and an alkaline waste liquid discharged in a zeolite synthesis step, wherein a siliceous to aluminosilicate activator (B) is used.
The soil modifying agent according to any one of claims 1 to 5, wherein the soil modifying agent comprises powdery granules of a filter cake generated when the mixture is neutralized with lime. 7. The soil modifier according to claim 1, wherein the siliceous to aluminosilicate activator (B) comprises waste clay used for refining oils and fats or a processed product thereof. . 8. The soil modifier according to claim 1, wherein the siliceous to aluminosilicate activator (B) comprises activated bentonite used as pet toilet sand. 9. The siliceous to aluminosilicate activator (B) contains an aluminum-containing zinc phyllosilicate or an amorphous silica complex thereof.
The soil modifier according to any one of the above.