JP2016117040A - Solidification material and solidification method of superfine powder inclusion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solidification material capable of obtaining a solidified body excellent in water repellency, when solidifying a kneaded product prepared by adding properly water to a superfine powder inclusion.SOLUTION: A solidification material is used for solidifying a superfine powder inclusion (treatment object) composed of or mainly composed of superfine powder by being added thereto or by being mixed therewith. The solidification material is composed of a main agent comprising cement (inorganic binder), and a sub agent comprising a water-repellency imparting agent. The water-repellency imparting agent contains a moisture-curable silicone oligomer, and properly another silane compound such as reactive silicone oil or fluoroalkyl arco silane.SELECTED DRAWING: None

Description

  The invention of the present application is made by adding and mixing to an ultrafine powder-containing material (processed material) such as sludge which is made of ultrafine powder such as a colloidal solid component or the like. The present invention relates to a solidifying material to be used and a solidifying method using the solidifying material.

  Here, ultrafine powder means an aggregate of particles of several μm or less (see Chemical Engineering Association, “Chemical Engineering Dictionary” (May 30, 1974) Maruzen, p410 “Crusher”). . The ultrafine powder includes not only particles but also fibrous materials such as asbestos of several μm or less.

  Sludge, etc. is limited to sludge (slurry material to be treated) composed of ultra fine powders such as silt and clay collected at the bottom of ponds, rivers and seas, humus soil containing organic matter, sludge, etc. Absent. Sludge and the like include mud, wall soil, rock ground, red soil, coal ash, slag, slag, incineration ash, pigments, and the like whose main production is ultra fine powder or aggregates thereof.

  Sludge and the like are composed of ultra fine powders (volcanic ash, coal ash, mineral powder, soot smoke, asbestos dust, etc.) harmful to the human body, and harmful heavy metals (for example, Cr (VI) Cd, Hg, Pb, As) in many cases.

  In order to solidify sludge and the like in the field of civil engineering and construction, a number of techniques related to solidifying materials such as mud using cement which is an inorganic binder have been proposed and implemented in Patent Documents 1 to 13 and the like. Yes.

  These technologies facilitate the transportation of sludge, etc. generated during the process of soil reinforcement and civil engineering / construction, prevent sewage from flowing out and scattering from the sludge during transportation, and the mud during the construction of rainwater. It is used for the purpose of preventing discharge due to river increase.

  Unlike the present invention, the technology related to the solidified material such as sludge described in Patent Documents 1 to 13 is not intended to impart water repellency positively. It does not contain a cured product and does not affect the patentability of the present invention.

  Further, in Patent Document 14, there is a curing auxiliary composition having a composition “comprising a vinyl alcohol polymer having a siloxane bond-forming side chain, a salt containing cobalt (II) chloride and an ammonium salt, and a nonionic surfactant”. It has been proposed (see abstract etc.).

  However, the silicone (organosilicon compound) in the curing auxiliary composition is a composition for obtaining a high-strength and non-water-absorbing solidified body (cured body) by mixing with a cement composition, and the present invention It does not affect the patentability of.

  The silicone in the present invention is a “siloxane whose side chain is a methyl group or a phenyl group”.

  On the other hand, the vinyl alcohol polymer in the same document has a siloxane bond-forming side chain, and the cured product (solidified product) partially has a siloxane bond. A polyethylene having a group or an acetate group ". For this reason, even if the “vinyl alcohol polymer having a siloxane bond-forming side chain” in Patent Document 14 is added to “cement”, and further, cobalt chloride, alkali chloride, alkali carbonate, etc. are added, the water repellency of the present invention is also achieved. It is considered that non-water absorption (low water absorption) cannot be achieved. Incidentally, in the SP value (solubility parameter), polyvinyl alcohol is 12.60, whereas dimethylsiloxane is 7.3 (polyethylene is 7.9) (Adhesion Handbook (2nd edition) edited by Japan Adhesion Association) (Sho 55-11 -10) See p.110).

  Therefore, Patent Document 14 does not affect the patentability of the present invention, similarly to Patent Documents 1 to 13.

  Furthermore, the solidified body (cured body) obtained by adding the solidified material of Patent Documents 1 to 14 to sludge or the like can provide a certain degree of strength (compressive strength), water repellency or non-water absorption, We do not plan to disintegrate the solidified product in water (resludge resistant to re-sludge), and we do not plan to suppress elution of harmful substances such as hazardous heavy metals.

Japanese Patent Application Laid-Open No. 7-136693 JP-A-8-071598 JP 2000-61424 A JP 2000-176493 A JP 2001-182044 A JP 2002-282894 A JP-A-2005-13973 JP 2005-131595 A JP 2006-137840 A JP 2008-94901 A JP 2008-55301 A JP 2009-214083 A JP 2013-107966 A Japanese Patent Application Laid-Open No. 2004-210588

  In view of the above, the present invention is to provide a solidified material capable of obtaining a solidified body having excellent water repellency when a kneaded material prepared by appropriately adding water to a material containing ultrafine powder is solidified. The first purpose.

  The second object of the present invention is to provide a solidified material that has excellent water repellency, high strength, non-water-absorbing properties, is resistant to disintegration in water, and is capable of obtaining a solidified body capable of suppressing elution of harmful heavy metals. It is to provide.

  The third object of the present invention is not dependent on organic materials such as fluororesins that have been widely used as water repellency imparting agents and polymer flocculants that have been frequently used as flocculants (Patent Documents 2 and 6). It is another object of the present invention to provide a solidified material capable of obtaining a solidified body having a deterioration resistance to withstand light, heat and radiation.

  As a result of diligent development in order to solve the above problems, the present inventor has come up with a solidified material and a solidified method having the following constitution.

The solidifying material according to the present invention is used to add and mix into an ultrafine powder-containing material (object to be processed) and solidify, and is composed of a main agent made of cement (inorganic binder), a water repellency imparting agent, and a curing auxiliary agent. A solidifying material comprising an auxiliary agent containing
The water repellency-imparting agent is a silicone composition comprising or mainly composed of a moisture-curable silicone oligomer (hereinafter referred to as “silicone oligomer”).

  In the solidifying material according to the present invention, it is preferable that the curing aid includes at least one of a curing accelerator, a Bacillus formation accelerator, and an interparticle hydration bond reducing agent.

Furthermore, the solidifying material according to the present invention may be configured such that, in the above configuration, the curing accelerator includes CaCl ₂ , the Bacillus formation accelerator includes CoCl ₂ , and the interparticle hydration bond reducing agent includes citric acid. desirable.

The solidification method according to the present invention is a method of solidifying the ultrafine powder-containing material using the solidification material having the above-described configuration,
(1) A step of adding water appropriately to the ultrafine powder-containing material (object to be treated) together with the silicone composition of the solidified material to form a uniformly dispersed slurry,
(2) A step of adding the cement of the solidifying material to the slurry and mixing to obtain a uniformly dispersed kneaded material, and curing the cured material under normal temperature or low temperature heating / pressurizing conditions to obtain a solidified body. It is characterized by having.

  Next, effects of the present invention will be described.

  In recent years, the amount of industrial waste such as coal ash, asbestos, and bauxite residue has increased, and it has become difficult to secure a disposal site.

  If the solidification material of this invention is used, the valuable solidified body which can be utilized effectively in the field of civil engineering and construction without relying on a disposal process for the sludge etc. which contain these industrial wastes is obtained. That is, the solidified body has excellent water repellency as well as high strength and non-water-absorbing properties, has a water disintegration resistance, and can suppress elution of heavy metals that are harmful substances.

  In addition, the solidified product obtained by using the solidified material of the present invention (if not powdered, pulverized) is again heated at room temperature or low temperature to the kneaded product prepared by adding the solidified material of the present invention and water. -If cured by curing under pressure, a reinforced solid with higher strength can be obtained. In this way, it is possible to expand the use of industrial sludge as a raw material in the civil engineering and construction fields.

  The method for producing a solidified body of the present invention comprises adding a solidified material of the present invention to a fine powder-containing material (processed material) such as sludge, and appropriately adding water to prepare a kneaded material at room temperature or low temperature heating / heating. There is also a production advantage that a solidified body is obtained by curing by a simple method of pressing.

  Hereinafter, embodiments of the present invention will be described in detail. In the following description, “parts” and “%” indicating the blending units mean “parts by mass” and “% by mass” unless otherwise specified.

  A. The solidifying material according to the present invention includes a main agent composed of <(1) cement (inorganic binder)> and an auxiliary agent composed of <(2) water repellency imparting agent> and <(3) curing aid>. As appropriate, it contains <(4) other auxiliary agent>. And a hardening adjuvant contains at least 1 sort (s) or more of a hardening accelerator, a Bacillus formation promoter, and an interparticle hydration bond reducing agent.

<(1) Cement (inorganic binder)>
As the cement (inorganic binder), hydraulic cement (including latent hydraulic cement) is usually used, but pneumatic cement (gypsum, lime) may be used. Examples of the hydraulic cement include Portland cement (including mixed Portland cement) and blast furnace slag cement. In addition, a pneumatic cement can also be mixed with a hydraulic cement in order to accelerate the setting reaction.

  Here, the mixing ratio of cement to sludge (containing ultrafine powder) cannot be limited by the type and density of sludge, the water content of sludge, and the like. In proportion to the amount of cement, the strength of the solidified body (uniaxial compressive strength) and water disintegration resistance (resludge resistance) tend to be improved.

<(2) Water repellency imparting agent (curable silicone composition)>
Here, the silicone composition contains silicone as a main component and alkoxysilane, which is a precursor thereof.

  As a water repellency imparting agent, moisture-curing silicone oligomer (hereinafter “silicone oligomer”) (I) is essential, and with silicone oil (II), fluorine-containing organic group alkoxysilane (III) or alkoxysilane (IV) as appropriate, A curable silicone (composition) containing the surfactant (V) is appropriately used. In general, it is desirable to use a silicone oligomer to which a curing catalyst is added. When a curing catalyst is not added, it is added and used.

(I) Silicone oligomer:
A partial hydrolysis condensate of the alkoxysilane compound represented by the general formula (1) is desirable.
R ¹ _x Si (OR ² ) _4-x (1)
However, R ¹ : H or a monovalent hydrocarbon group, R ² : an alkyl group, x: an integer of 0 to 3 (preferably 1 to 3) (Note that R ¹ and R ² are the same or different).

The monovalent hydrocarbon group for R ¹ is preferably a C1-C18 alkyl group, a C3-C8 cycloalkyl group, a C6-C8 aryl group, or a C7-C8 aralkyl (arylalkyl) group.

Specifically, it is as follows.
-Alkyl groups: methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, sec-pentyl, hexyl, heptyl, n-octene, isooctyl, 2- Ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl ・ Cycloalkyl group: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,
Aryl group: phenyl, tolyl, xylyl,
Aralkyl group: 1-phenylethyl, 2-phenylethyl, o, m or p-methylbenzyl,

  The monovalent hydrocarbon group may be one in which a hydrogen atom is substituted with a functional group (reactive group). Examples of the functional group include a halogen atom (for example, chlorine, fluorine, bromine and iodine), a hydroxyl group, a cyano group, an amino group, a carboxyl group and the like. These functional groups can be expected to improve water repellency by reacting with ultrafine powder particles or cement constituents (lime and clay).

The alkyl group for R ² is preferably a C1-C4 alkyl group. Specific group names include those exemplified as C1 to C4 among the aforementioned C1 to C18.

  Specific examples of the alkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, diphenyldimethoxysilane, and phenylmethyldimethoxysilane. , Tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, or a mixture thereof.

  Examples of commercially available silicone oligomers containing a curing catalyst include “KR-251” and “KR-400” (the above are trade names manufactured by Shin-Etsu Silicone Co., Ltd.). These can be emulsified in combination with a surfactant.

  Examples of commercially available silicone oligomers that do not contain a curing catalyst include "KR-242A", "KR-500", "KR-213", and "KC-89" (trade names manufactured by Shin-Etsu Silicone Co., Ltd.). Etc.

  Furthermore, you may use the commercial item of the silicone oligomer which contains the curing catalyst and was made into the emulsion (hydrosol). Examples of commercially available products include “SILRES BS SMK 2101J”, “SILRES BC 2103” (the trade name of Asahi Kasei Wacker Silicone Co., Ltd.) and the like.

  Moreover, “SILRES BS POWDER A” (trade name, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) can be cited as a commercially available silicone oligomer powder. When these come into contact with water, they undergo a dealcoholization reaction to form a cured silicone, and are usually blended in an uncured state.

  In addition, the said silicone hardened | cured material (powder) can also be used with a silicone oligomer. Examples of commercially available products of the cured silicone include “KMP-590”, “KMP-701”, “X52-854”, “X52-1621” (the trade name of Shin-Etsu Silicone Co., Ltd.).

  When each of the above silicone oligomers (excluding the silicone cured product) does not contain a curing catalyst in advance, a curing catalyst is added.

  When the silicone oligomer alone acts on the cement, the blending amount of the silicone oligomer is preferably 10 parts or less, more preferably 5 parts or less with respect to 100 parts of the cement. If the silicone oligomer is excessive, the strength of the solidified body may be adversely affected.

  The curing catalyst is not particularly limited. For example, the following organometallic compounds, inorganic acids, organic acids, inorganic bases, and amines can be mentioned. Of these, organometallic compounds are desirable. The amount of the curing catalyst added to the silicone oligomer varies depending on the type of catalyst, the type of silicone oligomer, and the like. Usually, 1 to 15 parts of the curing catalyst is used per 100 parts of the silicone oligomer.

(1) Organometallic compounds ・ Organic tin type: dibutyltin acetate, dibutyltin octylate, dibutyltin dilaurate, etc.
・ Organic aluminum system: aluminum tris (acetylacetone), aluminum tris (acetoacetate ethyl), aluminum diisopropoxy (acetate ethyl), etc.
Organic zirconium series: zirconium (acetylacetone), zirconium tris (acetylacetone), zirconium tetrakis (ethylene glycol monomethyl ether), zirconium tetrakis (ethylene glycol monobutyl ether), etc.
Organic titanium: titanium tetrakis (ethylene glycol monomethyl ether), titanium tetrakis (ethylene glycol monoethyl ether), titanium tetrakis (ethylene glycol monobutyl ether), etc.

(2) Inorganic acids hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc.

(3) Organic acids Formic acid, acetic acid, oxalic acid, trifluoroacid, etc.

(4) Inorganic base Ammonia, sodium hydroxide, potassium hydroxide, etc.

(5) Amines (including derivatives)
Ethylenediamine, alkanolamine, amino-modified silicone, aminosilane, silazane, etc.

  Among these, inorganic acids, organic acids, and inorganic bases are preferably not used if possible because they may inhibit the condensation reaction of cement (inorganic binder).

  Examples of commercially available organometallic compounds include “D-20” for titanium, “D-15” for zinc, and “CAT-AC” for aluminum (trade name of Shin-Etsu Silicone Co., Ltd.). It is done.

(II) Silicone oil:
Non-reactive silicone oil represented by the following general formula (2), (3) or (4), and represented by the following general formula (5), (6), (7), (8), and (9) There are reactive silicone oils. Of these, reactive silicone oil is desirable. In addition, the range of m and n in each following chemical formula is not specifically limited. The ranges of m and n are set so as to indicate the kinematic viscosity (20 ° C. kinematic viscosity) (for example, 1 to 100000 mm ² / s) in a commercial product of each silicone component.

However, R < ³ >: A methyl group, m, n: The same or different arbitrary integers.

However, R ^4: methyl, R ^5: a phenyl group, m, n: the same or different arbitrary integers.

However, R ^6: a methyl group, n: integer.

Where R ^{7 is a} methyl group, R ^{X is a} functional group-substituted hydrocarbon group, m, n are the same or different arbitrary integers.

  Here, examples of the functional group-substituted hydrocarbon group include an alkyl group substituted with an amino group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, a phenyl group, and the like.

Where R ^{8 is a} methyl group, R ^{X is a} functional group-substituted hydrocarbon group, and n is an arbitrary integer.

  Examples of the functional group-substituted hydrocarbon group include those similar to the general formula (5).

Where R: hydrocarbon group, R ⁸ : methyl group, R ^X : functional group-substituted hydrocarbon group, n: any integer.

  Examples of the functional group-substituted hydrocarbon group include those similar to the general formula (5).

However, R ^9: a methyl group, R ^X: functional group substituted hydrocarbon group, m, n: the same or different arbitrary integers.

  Examples of the functional group-substituted hydrocarbon group include those similar to the general formula (5).

R ¹⁰ and R ^{11 are} monovalent hydrocarbon groups, m is an integer of 0 to 2, and n is an integer of 0 to 400 (preferably 5 to 250) (R ¹⁰ and R ¹¹ are the same or different).

  Examples of commercially available reactive silicone oils include “X-22-173BX”, “X-22-170BX”, and “X22-174ASX” (all of these are trade names manufactured by Shin-Etsu Chemical Co., Ltd.). It is done.

  These reactive silicone oils may be used alone or in combination of two or more.

  Emulsified silicone oil products are "TSW831" as a methyl hydrogen type (curing accelerator added product) (trade name manufactured by Momentive Performance Materials Japan GK), "KP2601" as an amino-modified type, “NP2609” (trade name, manufactured by Asahi Wacker Silicone Co., Ltd.).

  Further, as the non-reactive silicone oil, a solid / particulate one can be used. Examples of the commercially available product include fine particle “X52-1621” (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.). In addition, non-reactive silicone oil has the effect of imparting water repellency to the solidified body as well as other silicone components, but when used as a solidifying material component, the compatibility with other solidifying material components is poor and, if possible, a blending component It is desirable not to.

  The blending amount of the silicone oil with respect to 100 parts of the silicone oligomer is desirably 5 parts or less, more preferably 3 parts or less. When the blending amount of silicone oil is large, it is difficult to obtain practical strength in the solidified body, or it becomes difficult to maintain the form of the emulsion.

(III) Fluorine organic group alkoxysilane:
A fluoroalkylalkoxysilane represented by the following general formula (10) is desirable. These can be used alone or in admixture of two or more. In the general formula (10), a fluoropolyether type fluorine organic group alkoxysilane in which “CF ₂ ” is “—O—CF ₂ ” and “x = 1 to 10” may be used.

However, R ^12: alkyl group or alkoxyl group C1~4, R ^13, R ^14: an alkoxyl group (same or different), x: 0 integer, Y: 0 to 2 integer.

Examples of the alkyl group represented by R ¹² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group.

Examples of the alkoxyl group represented by R ¹² , R ¹³ , and R ¹⁴ include C1 such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, and t-butoxy group. -C4 alkoxyl group is mentioned. Of these, it is desirable that all of R ¹² , R ¹³ and R ¹⁴ are methoxy groups. These fluoroalkylalkoxysilanes may be used alone or in combination of two or more.

  Specific compound names include perfluorohexylethyltrimethoxysilane, perfluorooctylethyltrimethoxysilane, perfluoroheptylethyltrimethoxysilane, perfluorobutylethyltrimethoxysilane, perfluoropropylethyltrimethoxysilane, perfluoro. And ethyl ethyltrimethoxysilane.

  The blending amount of fluoroalkylalkoxysilane with respect to 100 parts of silicone oligomer is preferably 10 parts or less, and more preferably 5 parts or less. If the blending amount of the fluorine-containing alkoxysilane compound exceeds 10 parts, the hydrosol state may not be maintained.

(IV) Alkoxysilane:
Examples thereof include monoalkoxysilane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane represented by the following general formula (11). Of these, trialkoxysilane is desirable.

However, R ^A : alkoxyl group, R ^B , R ^C , R ^D : alkyl group or alkoxyl group (same or different)

  Desirable alkoxysilane compounds include hexyltrimethoxysilane, heptyltrimethoxysilane, butyltrimethoxysilane, propyltrimethoxysilane, and the like.

  These alkoxysilane compounds may be used alone or in combination of two or more.

  The amount of other silicone components (silicone oil, fluorine organic group alkoxysilane, alkoxysilane) added to 100 parts of the silicone oligomer in the silicone composition is preferably 5 parts or less, more preferably 3 parts or less. When the amount of the other silicone component is large, the strength of the solidified body may be reduced, and the resistance to disintegration in water (resistance to re-sludge) may be reduced.

(V) Surfactant:
In order to mix the silicone composition of the present invention, including each component, in the form of an emulsion, when using a silicone component to which no surfactant is added, a surfactant is added.

  The surfactant is not limited as long as it can stably maintain an emulsion (hydrosol) of silicone. The following cationic and anionic compounds can be preferably used.

  Cationic system: alkylamine salt, quaternized ammonium salt, ethylene oxide addition type quaternized ammonium chloride, and the like.

  Nonionic: polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, and the like. Of these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester are desirable.

  These surfactants may be used alone or in combination of two or more.

  More specifically, “Lionol TDL20 / TDL30” is used as polyoxyethylene alkyl ether, “Esomeide HT16”, “Esomeide O15” (amide) (trade name, manufactured by Lion Co., Ltd.), etc. are used as polyoxyethylene alkylamide. Can be mentioned.

<(3) Curing aid>
A curing aid is added to the solidified material of the present invention in order to obtain practical strength in the solidified body.

  The curing aid preferably contains at least one of a curing accelerator (I), a Bacillus formation accelerator (II), and an interparticle hydration bond reducing agent (III). Each component is appropriately selected depending on the type of the object to be processed.

  In the case where high strength and non-water absorption (water-tightness) are required to ensure water-repellent, water-disintegration resistance and suppression of harmful heavy metals elution, the solidifying material is a curing accelerator, It is desirable to contain all the components of the Bacillus formation accelerator and the interparticle hydration bond reducing agent.

  Further, when the object to be treated is a floating ultrafine powder, it is desirable to further add a flocculant.

  In addition, the amount of the additive that inhibits the binding property of the silicone composition to the cement or ultrafine powder and the water repellency of the solidified body among the curing aids is reduced as much as possible.

  Moreover, what was illustrated as a suitable compound for each hardening adjuvant by the following description does not necessarily show | play only the effect | action of each hardening | curing agent auxiliary component, but may show | play other actions simultaneously.

For example, FeCl ₃ that acts as a Bacillus formation accelerator also acts as an agglomerating agent for ultrafine powder. NaCl, K ₂ CO _{3 which} acts as an interparticle hydration bond reducing agent also acts as an auxiliary to the Bacillus formation accelerator. Further, weakly alkaline Na ₂ CO ₃ and K ₂ CO ₃ , weakly acidic MgCl ₂ and CaCl ₂ can also serve as a pH adjuster.

(I) Curing accelerator When added to the ultrafine powder-containing material and solidified, it is necessary to ensure the strength of the obtained solidified body. In the case of slag cement, in advance, for a curing auxiliary agent in the present invention (MgCl _2, MgSO _4, etc.), formulated on it is not necessarily of adding.

Specifically, CaCl ₂ , MgCl ₂ (especially CaCl ₂ ) and the like can be preferably used as the curing accelerator, but CrO ₄ ²⁻ , S ₂ O ₄ ²⁻ Ca salt, diffusion coefficient and water high solubility chloride (Cl ^- ion compounds) can also be used (edited by the chemical Society of Japan, "fifth Edition chemical Handbook applied chemistry edited by I" (flat 7-3-15) Maruzen, P394, see Table 5.58).

  The blending ratio of these curing accelerators in the curing aid varies depending on the type of curing accelerator and is not particularly limited. For example, it is appropriately selected within a range of 10 to 80%.

(II) Bacillus processing aids and (cement) Bacillus that of ettringite _{(3Ca0 · Al 2 O 3 ·} 3CaSO 4 · 32H 2 O) (Ca -based needle crystals), water resistance of the Ca-based needle into solidified By forming the crystals and filling the pores of the solidified body with these needle-shaped crystals, the solidified body is prevented from collapsing in water (re-sludge) and the elution from the solidified body such as heavy metals is suppressed. It is necessary to be.

As this Bacillus formation accelerator, iron group element chloride can be used, and FeCl ₃ or the like may be used, but CoCl ₂ is desirable. Metal chlorides (MgCl ₂ , NaCl, FeCl ₃ etc.) and alkali carbonates are used as secondary components.

The ratio of the Bacillus formation accelerator in the solidified body is not particularly limited because there is a relationship with other curing aids. The blending ratio of CoCl ₂ in the curing aid is desirably 3 to 12%.

(III) Interparticle hydration bond reducing agent As the hydration bond reducing agent, citric acid is desirable among the oxycarboxylic acids used as setting retarders in cement admixtures. Oxycarboxylic acids other than citric acid, such as gluconic acid, tartaric acid, malic acid and the like, have the possibility of use.

  The oxycarboxylic acid is bonded to a hydroxyl group and a carboxyl group on the cement surface to delay the hydration of the cement, to prevent a decrease in denseness due to rapid curing and to secure a solidified body strength. In this invention, there exists an effect | action which reduces the hydration bond between microparticles | fine-particles of a to-be-processed object, and does not inhibit the hydration (bonding) reaction of cement Ca component.

  Conventionally, it is not possible to obtain sufficient practical strength for solidified bodies even when hardened red soil (strong interparticle hydration bond) or mountainous or field soil containing a high amount of organic matter (caustic) with cement. It was common knowledge to those skilled in the art. That is, if the cement contains an organic substance (especially a saccharide), the hydration reaction is delayed, and if the amount of saccharide increases, it will eventually not set.

  It has been found that the solidified product of red soil and upland soil can be obtained by using citric acid among oxycarboxylic acids conventionally used as setting retarders. At this time, it was also found that it is desirable to use a relatively large amount of strong electric field in combination.

The reason is that “the concentration of strong electric field containing K ⁺ , Na ^+, or Mg ²⁺ increases the hydration property, and the adsorptive water attractive force between the ultrafine powder particles decreases, and the agglomeration of the aggregates. Because of this, Ca ²⁺ (cement) enters between red soil and ultrafine powder particles, and cement acts as a binder. ”

Na ⁺ and Ka ⁺ (1 genus, 2 and 3 periods) have a small ion diameter, and Mg ²⁺ and Ca ²⁺ (1 genus and 2 and 3 periods) have a relatively small ion diameter and ions. High value and easy to hydrate (see “Inorganic Chemistry” Kanie Publishing, p139 “§9.9 Properties of Strong Electrolyte Solutions”).

Specific strong electrolyte, can be cited NaCl, KCl, and _{MgCl 2, CaCl 2, Na 2} CO 3, K 2 CO 3, Na 2 SO 4, K 2 SO 4 and the like.

  The mixing ratio of the interparticle hydration bond reducing agent in the curing aid is desirably 2 to 5% in the case of citric acid.

<(4) Other side agents>
In addition to the silicone composition (water repellency imparting agent) to the cement, and in addition to the curing aid, other known additives used as conventional cement admixtures can be appropriately selected and used ( The Chemical Society of Japan, “Chemical Handbook Application, Revised 3rd Edition” (Akira 55-3-15) Maruzen, p394, Table 5.58). Admixtures are those that contribute to improving the physical properties of solidified bodies such as concrete produced using cement.

That is, for the solidifying material, an admixture conventionally used in cement, such as a flocculant, a pH adjuster, a high moisture absorbent, a thickener (PVAL), an antifoaming / dispersing agent, and a pigment, It can be blended. As the flocculant, a polymer flocculant can be used, but an inorganic flocculant such as FeCl ₃ is desirable because it is hardly affected by radiation or the like.

  Moreover, when manufacturing the concrete solidified body which distributes a steel frame, it is desirable to contain nitrite, a rhodanate, and a phosphate with a metal ion removal effect for a steel-frame corrosion prevention (rust prevention).

  The blending amount of the other auxiliary agent is not limited and may be in a range that does not inhibit the strength of the solidified body.

  In addition, the solidified material of the present invention is blended with reinforcing materials such as paper fibers, plastic fibers, glass fibers, carbon fibers, metal fibers, and aggregates such as gravel at the time of production of the solidified bodies. Effects such as strength enhancement and prevention of cracking can be obtained, and the use range of the solidified body can be expanded.

  B. A method for producing a solidified body using the solidified material of the present invention will be described.

  (1) Water is added to a predetermined amount of sludge (object to be treated) put in a mixing vessel such as a mixer together with the silicone composition of the solidified material to obtain a uniformly dispersed slurry (sludge).

  (2) A solidified cement (inorganic binder) is added to the slurry and mixed to obtain a uniformly dispersed kneaded product. The kneaded product is poured into a mold of an arbitrary size and cured under normal temperature or low temperature heating / pressurizing conditions to produce a solid body in the form of a lump, granular or form block.

  The order of adding the silicone composition and cement is not limited to the above, but if cement is added before the silicone composition is added, the dissolution and dispersibility of the cement may be reduced.

  The solidified body produced above has strength and water repellency, as well as resistance to disintegration in water and leaching of harmful heavy metals. That is, since the cured product of the silicone composition of the present invention is stable to light, heat, and radiation, the solidified body has excellent water repellency or non-water absorption in a wide range of use environments, and further is resistant to water. It also provides disintegration (non-remudability) and long-term strength maintenance.

  For this reason, it is excellent in the storage stability in the case of isolating and storing for a long time using sludge containing a large amount of pollutants as a solidified body. In particular, it is effective when applied to sludge containing a large amount of harmful substances such as asbestos, radioactive substances and heavy metals.

  Moreover, the solidified body manufactured by this invention can be pulverized as it is or appropriately, and can be used for soil modifiers, landfill work, fishing reefs, and the like.

  Furthermore, the solidified product produced as described above can be a regenerated solidified product with higher strength as described below.

  The solidified product is appropriately pulverized to obtain a pulverized product having a particle diameter adjusted to a predetermined range. A predetermined amount of the solidifying material of the present invention and water are added to the crushed product to obtain a kneaded product. At this time, if necessary, the solidified material is used in combination with various aggregates / reinforcing materials other than the solidified body, and the kneaded material is prepared and poured into a predetermined formwork, and heated or heated at normal or low temperature. By performing curing and curing under pressure conditions, it is possible to produce a regenerated solidified body derived from sludge with higher strength.

  For this reason, the manufacturing method of the reproduction | regeneration solidification body of this invention can expand application to the civil engineering construction field | areas, such as a steel concrete material and also a tile, a block, a roadbed material.

  Next, the present invention will be described with reference to test examples including examples, but the present invention is not limited to the following test examples.

<Raw material ingredients>
Each component raw material used in the test example is as follows.
(A) Cement (binder)
A1: Commercial Portland cement,
Composition: SiO ₂ : 21.1%, Al ₂ O ₃ : 5.3%, Fe ₂ O ₃ : 2.4, CaO: 66.2, MgO: 1.6%
SO ₃ : 2.3%, Na ₂ O: 0.3%, K ₂ O: 0.4%, TiO ₂ : 0.1%
A2: Blast furnace slag cement,
Composition _{... MgO: 3.31%, SO 3} : 2.05%, Cl -: 0.01%

(B) Moisture curable silicone oligomer B1: "KR-400" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), viscosity 1.2 mPa.s / 25 ° C, specific gravity 0.98 / 25 ° C,
-B2: "SILRES BS SMK 2101J" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), viscosity 1-10 mPa.s / 25 ° C, specific gravity 0.9 / 25 ° C,
・ B3: “SILRES BS POWDER A” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), octyltriethoxysilane / silica type, bulk specific gravity 500 kg / m ² ,

(C) (Reactive) Silicone oil C1: “X-24-9377” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), methoxy type, viscosity 6 mPa.s / 25 ° C.
C2: “X52-1621” (manufactured by Shin-Etsu Silicone Co., Ltd.), spherical silicone oil, average particle size 5 μm, true specific gravity 0.99,

(D) Fluorine-containing silane (fluoroalkylsilane)
D: perfluorohexylethyltrimethoxysilane,

(E) Alkoxysilane:
E: Hexyltrimethoxysilane,

(F) Surfactant F: Nonionic surfactant (polyoxyethylene alkyl ether),

(G) a curing aid _{· GM: CaCl 2, KCl,} NaCl, CaCl 2, MgCl 2, FeCl 3, K 2 CO 3, citric acid, Na ₂ SO ₄ (total 100 parts)

(T) Aggregate:
・ Dry river sand (φ0.5-5.0mm)

(R) Reinforcing material:
・ Glass fiber (average fiber length: 13 mm, filament diameter: 10 μm),

(H) Sludge, etc. (processed object):
・ Coal ash (moisture 27.0%)
・ Red soil (moisture 27.0%)

(S) Radioactive material:
・ "IOMIX Powder" Brand name, 1kg / dose equivalent (2.650μSv / h, measuring distance: 10mm, measuring humidity: 60%), manufactured by Mino Pigment Chemical Co., Ltd.

<Preparation of silicone (composition)>
The silicone oil, fluoroalkylsilane, alkoxysilane or surfactant shown in Table 1 was added to the silicone oligomer in the indicated formulation and mixed with a homogenizer to prepare 500 g of each silicone composition. The mixing operation was performed at a homogenizer rotation speed of 5000 rpm and mixed for 3 minutes. These silicone compositions were easily emulsified.

<Preparation of curing aid>
Using a Waring-type mixer ("DB2264", a product name manufactured by Kaiin Co., Ltd.), each component (compound) of the curing adjuvant listed in Table 2 is uniformly mixed and dispersed in the formulation shown in the same table to assist in curing. Agent (GM) was prepared.

<Creation of specimens for comparative examples and examples>
Add the silicone composition of the solidifying material and the curing aid (only the curing aid in the comparative example) to the coal ash or red clay in the formulation shown in Table 3 or Table 4 (1) to (4), and further solidify A kneaded material was prepared by adding the cement of the material together with water (water / cement ratio 0.55). The kneaded product is poured into a mold of φ50 × 100 mm, demolded after being left at room temperature for 3 days, and then air-dried for 25 days to prepare each specimen of Comparative Examples 1 to 4 and Examples 1 to 34. did.

<Creation of test specimen of application example>
After the crushed material of the test body (solidified body) prepared in Examples 1, 2, 23, and 24 was adjusted to a particle diameter of 0.5 to 5.0 mm with a sieve, a silicone composition and a curing aid were used as a solidifying material. Then, a kneaded product was prepared by adding cement with water (water / cement ratio 0.55). The kneaded product was poured into a mold of φ50 × 100 mm, left to stand at room temperature for 3 days, demolded, and then air-dried for 28 days to prepare test specimens of application examples 1 to 4.

<Physical property evaluation test method>
The test method performed in order to confirm the effect of this invention about each test body created by the comparative example, the Example, and the application example is demonstrated.

(1) Water repellency evaluation test The water repellency was measured by subjecting the specimen to air drying at room temperature for 28 days, then putting it in an air dryer maintained at 100 ° C. and drying it for 6 hours. It was carried out after storing in a desiccator.

  The test specimen taken out from the desiccator was immersed in water at 20 ° C. for 20 minutes and then lifted from the water, and the wet state of the surface was visually observed.

  Visual evaluation criteria for water repellency were as follows.

    A: Repels water and leaves no wet marks.

    ○: Plays water, but some blur marks remain.

    Δ: There is a part that flips water, but the blotting marks were confirmed to be 50% or more of the whole.

    X: No sign of playing water at all.

(2) Water absorption measurement test When the water absorption of the solidified body is high, the area of the solidified body in contact with water increases, and re-mudging tends to be promoted. Further, the water repellency and water absorption of the sludge solidified body have an inversely proportional relationship. Therefore, the water absorption was measured by the following procedure. The specimen was air-dried at room temperature for 14 days and then measured according to “JIS A5208 5.2”.

(3) Compressive strength measurement test If the strength of the sludge solidified body is large, there is an effect of expanding its use, so the compressive strength was measured by the following procedure.

  Each specimen was air-dried at room temperature for 14 days and then measured according to JIS A-1108.

<Evaluation test results>
(1) Tables 3 and 4 (1) to (4) show the test results of the comparative examples and examples.
From the test results, it was confirmed that the test specimens of each example of the present invention, except for Examples 13 and 14, were excellent in compressive strength, excellent in water repellency and low water absorption, and exhibited the effects of the present invention. did it.

  Examples 13 and 14 in which the silicone composition does not contain reactive silicone oil or fluoroalkylsilane have high compressive strength, but are slightly inferior in water repellency or non-water absorption to other examples.

  On the other hand, in comparison with Examples 13 and 14, the test bodies of Comparative Examples 1 and 3, which do not contain a curing aid together with the silicone composition, have a remarkably low compressive strength and water repellency or Non-water absorption is also poor.

(2) Table 5 shows the test results of the application examples.
From the test results, it can be seen that the regenerated solidified material prepared using the pulverized solidified material of the present invention is remarkably excellent in water repellency or non-water absorption as well as compressive strength as compared with each Example.

<Other characteristic evaluation tests and test results>
(1) Heavy metal elution measurement test If the heavy metals contained in the solidified body are eluted, the environment is contaminated. Therefore, the elution amount of heavy metal eluted from the solidified body was measured by the following procedure.

  About the test body of Example 5, the amount of elution of each metal element was quantitatively analyzed by the analysis method shown in Table 6. From Table 6 showing the analysis results, it was confirmed that the solidified product of the present invention has an effect of remarkably suppressing elution of heavy metals.

  In addition, Table 7 shows the metal content analysis values of coal ash used in Example 5 for reference.

(2) Confirmation test of deterioration due to radioactivity Whether the water repellent performance formed in the sludge solidified body is reduced by the radiation emitted from the radioactive material contained in the sludge solidified body, and the effect of radiation on the water repellent phenomenon In order to investigate, the test was conducted according to the following procedure.

  A test specimen was prepared in the same manner as described above by adding 3.0 parts of radioactive material to 96.40 parts of Portland cement and 0.60 part of the silicone composition (B2).

  The test specimen was fixedly installed outdoors from March 21, 2009 to October 27, 2012, exposed to wind and rain, and the water-repellent phenomenon during rainfall was continuously observed. As a result, there was no change in water repellency (◎) and water absorption rate (1.20%) during this period, and no significant change over time of about three and a half years was observed.

(3) Reference example (effect confirmation test of curing aid on solidified body)
Table 8 shows the compositions of the curing aids GM1 to GM9 excluding a part of the components of the curing aid (metal chloride, citric acid, cobalt chloride, carbonic acid / sulfuric acid alkali salt, etc.) added to the cement.

  And in the prescription of the comparative example 2 (Table 3) using each hardening adjuvant, the reference example test body was prepared like the comparative example 2 except having replaced the hardening adjuvant GM with the hardening adjuvants GM1-GM9. Similarly, water repellency evaluation, water absorption rate and compressive strength were tested.

The results are shown in Table 8. From the results, it can be seen that the Bacillus generator (CoCl ₂ ) is essential for securing the strength together with the curing accelerators (CaCl ₂ , KCl, MgCl ₂ ).

  Citric acid breaks the attractive force generated between the ultrafine powder particles and permeates and diffuses the calcium component of the cement solution between the particles, thereby contributing to an increase in strength of the solidified body. However, since the coal ash used in the test examples does not contain an organic component (humic acid or the like), the contribution rate to the strength increase is small. However, since GM8 containing no citric acid has the highest water absorption rate, it can be seen that citric acid has a non-water absorption increasing action (consolidating body densification action).

Metal chlorides other than CaCl ₂ assist the hardening (coagulation) reaction of cement, and CoCl ₂ forms needle crystals with Na ₂ SO ₄ , calcium components of cement, etc. It is thought that there is also an effect of increasing sex.

(4) Additional test example I (Practicability confirmation test of air-hardening cement)
From the knowledge of the present inventor who added citric acid to anhydrous gypsum and solidified red clay for air-cemented cement, a curing aid GM containing all other components along with citric acid was added to slaked lime (stucco), A solidified body was made by solidifying the soil and red soil. The solidified body was submerged in the ocean and tested for resistance to disintegration in water. In this test, a temporary result was obtained, but when anhydrous gypsum contains foreign matter, Bacillus is excessively generated depending on the curing conditions (temperature and humidity), and it may be difficult to obtain a practical strength. For this reason, when using together a hardening adjuvant, it is necessary to adjust a mixing | blending, but it has confirmed that it was possible to provide water repellency to a pneumatic cement with a silicone composition.

  And the solidified product of additional test examples I-1 and I-2 prepared by blending and curing the silicone composition B3 in anhydrous gypsum or slaked lime, and the curing aid or field only of red clay, anhydrous gypsum and citric acid The said evaluation test was done about the solidified body of the additional test examples I-3 to I-5 created by kneading in combination with soil, slaked lime, and a curing aid GM and curing in air.

  From Table 9 showing the results of the evaluation test, the silicone composition of the present invention sufficiently imparts water repellency. Further, from the additional test example I-3, even when the component of the curing auxiliary agent is citric acid alone, sufficient strength increasing action is obtained. I can hear you play.

(5) Additional Test Example II (Solidification confirmation test with organic sludge curing aid)
It was said that it was difficult to harden upland soil and mountain soil containing a large amount of organic matter with cement. Then, about the solidified body of the additional test examples II-1 to II-3 prepared by curing the field soil mixed with bagasse (sugar milled rice cake) with the cement A1 using the curing auxiliary agent GM of the present invention. The evaluation test was conducted. In addition, the amount of water required for the blended composition was adjusted to have a slump value of 20 to 22 cm.

  The results of the evaluation test are shown in Table 10. It has been confirmed that the curing aid containing citric acid of the present invention has a practical strength.

Claims (10)

It is used to solidify by adding to and mixed with ultrafine powder containing material (object to be processed), and solidifying consisting of a main agent consisting of cement (inorganic binder) and a secondary agent containing a water repellency imparting agent and a curing aid. Material,
The water repellency-imparting agent is a silicone composition comprising or mainly composed of a moisture-curable silicone oligomer (hereinafter referred to as “silicone oligomer”).
Solidified material characterized by that.   The solidifying material according to claim 1, wherein the silicone composition further contains at least one of silicone oil, fluorine organic group alkoxysilane, and alkoxysilane.   3. The solidified material according to claim 2, wherein the silicone oil is a reactive silicone oil, and the fluorine organic group alkoxysilane is a fluoroalkylalkoxysilane. The solidified material according to claim 1, 2, or 3, wherein the silicone oligomer is a partially hydrolyzed condensate of alkoxysilane represented by the following general formula (1).
R ¹ _X Si (OR ² ) _4-X (1)
(Wherein R ¹ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ² represents an alkyl group, and x is an integer of 0 to 3)   The solidifying material according to any one of claims 1 to 4, wherein the curing aid contains at least one of a curing accelerator, a Bacillus formation accelerator, and an interparticle hydration bond reducing agent. Wherein the curing accelerator is CaCl _2, wherein the Bacillus produces promoter of CoCl _2, solidifying material of claim 5 wherein said intergranular wettable bond reducing agent, characterized in that it comprises citric acid.   The solidifying material according to claim 6, wherein the curing accelerator further contains an alkaline metal salt, and the interparticle hydration bond reducing agent further contains an alkali carbonate.   The solidifying material according to claim 1, wherein the auxiliary agent further contains an inorganic flocculant. A method for solidifying the ultrafine powder-containing material using the solidifying material according to claim 1,
(1) A step of adding water appropriately to the ultrafine powder-containing material (object to be treated) together with the silicone composition of the solidified material to form a uniformly dispersed slurry,
(2) A step of adding the cement of the solidifying material to the slurry and mixing to obtain a uniformly dispersed kneaded material, and curing the cured material under normal temperature or low temperature heating / pressurizing conditions to obtain a solidified body. With
A method for solidifying an ultrafine powder-containing material.   A kneaded product prepared by adding the solidified material according to any one of claims 1 to 8 and water again to a crushed product of the solidified product obtained by the method according to claim 9 under normal temperature or low temperature heating / pressurizing conditions. A method for producing a regenerated solidified product, which is cured and cured to obtain a regenerated solidified product.