JPH08277174A - Clay-humic acid compound porous body and its production - Google Patents
Clay-humic acid compound porous body and its productionInfo
- Publication number
- JPH08277174A JPH08277174A JP10311195A JP10311195A JPH08277174A JP H08277174 A JPH08277174 A JP H08277174A JP 10311195 A JP10311195 A JP 10311195A JP 10311195 A JP10311195 A JP 10311195A JP H08277174 A JPH08277174 A JP H08277174A
- Authority
- JP
- Japan
- Prior art keywords
- clay
- humic acid
- porous body
- sol
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/001—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing unburned clay
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00112—Mixtures characterised by specific pH values
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、粘土−フミン酸複合多
孔体及びその製造方法に関するものであり、さらに詳し
くは、地球環境保全に配慮した緩衝材、断熱材、吸音材
等として有用な粘土−フミン酸複合多孔体及びその製造
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a clay-humic acid composite porous body and a method for producing the same, more specifically, a clay useful as a cushioning material, a heat insulating material, a sound absorbing material, etc. in consideration of global environmental protection. The present invention relates to a humic acid composite porous body and a method for producing the same.
【０００２】[0002]
【従来の技術】従来より、緩衝材、断熱材、或いは吸音
材等としては、軽量でかつ安価である等の理由からポリ
スチレン樹脂、ウレタン樹脂等の樹脂発泡体が広く一般
的に利用されている。しかしながら、これらの材料は、
化学的に安定であることから、地球上の生態系では分解
されず、仮に、不用意に河川や海浜などに廃棄された場
合、美観を損ね、環境を汚染するなどの問題を抱えてい
た。また、これら樹脂発泡体は、地球深部より人為的に
採掘された石油を原料としており、廃棄物の焼却に際し
ては、高熱を放出して焼却炉を破損し、同時に大量のガ
スを発生して地球環境汚染を引き起すという欠点があっ
た。2. Description of the Related Art Conventionally, as a cushioning material, a heat insulating material, a sound absorbing material, etc., resin foams such as polystyrene resin and urethane resin have been widely and generally used because they are lightweight and inexpensive. . However, these materials
Since it is chemically stable, it is not decomposed in the earth's ecosystem, and if it is accidentally disposed of in rivers or beaches, it has a problem of spoiling the aesthetics and polluting the environment. In addition, these resin foams are made from petroleum that has been artificially mined from deep inside the earth, and when incinerating waste, it emits high heat and damages the incinerator, and at the same time generates a large amount of gas to generate a large amount of gas. It had the drawback of causing environmental pollution.
【０００３】この様な実状に鑑み、本発明者らは、緩衝
材、断熱材、吸音材等の材料として用いられているポリ
スチレン等を代替する地球環境親和素材の実用化を目的
とし、粘土ゾルを急速凍結し、融解することなく乾燥し
て得られる粘土多孔体を出願した（特公平４−１７９１
３号）。このものは環境汚染がなく、吸着能、触媒能に
優れたものであるが、多孔体の強度、特に圧縮強度が若
干不足し、実用化には未だ十分なものではなかった。In view of these circumstances, the present inventors have aimed to put a clay sol into practical use in order to put into practical use a global environment friendly material that substitutes polystyrene used as a material for a cushioning material, a heat insulating material, a sound absorbing material and the like. Applied for a clay porous body obtained by rapidly freezing and drying without melting (Japanese Patent Publication No. 4-1791).
No. 3). This product has no environmental pollution and is excellent in adsorption ability and catalyst ability, but the strength of the porous body, particularly the compression strength, is slightly insufficient, and it is not sufficient for practical use.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、従来技術よ
り見られる前記問題を解決し、回収再利用が容易で、廃
棄するに際しては、天然の土壌に容易に変換され、生態
系の中に組込まれる地球環境親和素材のみからなり、平
均細孔径が小さく、圧縮強度に優れ、緩衝材、断熱材、
吸音材等として有用な粘土−フミン酸複合多孔体及びそ
の工業的に有利な製造方法を提供することをその課題と
する。DISCLOSURE OF THE INVENTION The present invention solves the above problems found in the prior art, is easy to recover and reuse, and is easily converted into natural soil when it is discarded, and it is easy to use in the ecosystem. Made of only materials that are compatible with the global environment, have a small average pore size, excellent compressive strength, cushioning materials, heat insulating materials,
It is an object of the present invention to provide a clay-humic acid composite porous body useful as a sound absorbing material and the like and an industrially advantageous production method thereof.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、従来技術
より見られる前記問題を解決すべく鋭意研究を重ねた結
果、特定の濃度の粘土ゾル、並びにフミン酸溶液を、特
定のｐＨ値に調整し、特定の混合比（重量比）により混
合せしめ、急速凍結し、次いでこの凍結体を融解するこ
となく乾燥して得られる多孔体が有効であることを見い
出し、本発明を完成するに至った。すなわち、本発明に
よれば、第一にフミン酸成分が２０〜４０ｗｔ％、平均
細孔径が０．８μｍ〜２．０μｍであり、圧縮強度が、
３．００ｋｇｆ／ｃｍ2以上であることを特徴とする粘
土−フミン酸複合多孔体が提供され、第二に、粘土濃度
が５〜１５ｗｔ％の粘土ゾルとフミン酸濃度が５〜１５
ｗｔ％のフミン酸溶液とを、粘土成分とフミン酸成分と
の混合（重量）比が、８：２〜６：４の割合で混合して
混合ゾルを得、ｐＨが４〜８の該混合ゾルを１×１０2
ｍｌ／秒以上の平均凍結速度で急速凍結し、次いで融解
することなく乾燥することを特徴とする粘土−フミン酸
複合多孔体の製造方法が提供される。Means for Solving the Problems As a result of intensive studies to solve the above problems found in the prior art, the present inventors have found that a clay sol having a specific concentration and a humic acid solution have a specific pH value. In order to complete the present invention, it was found that a porous body obtained by adjusting the mixture to a specific mixing ratio (weight ratio), rapidly freezing, and then drying this frozen body without thawing is effective. I arrived. That is, according to the present invention, firstly, the humic acid component is 20 to 40 wt%, the average pore diameter is 0.8 μm to 2.0 μm, and the compressive strength is
Provided is a clay-humic acid composite porous body, which is characterized by being 3.00 kgf / cm 2 or more, and secondly, a clay sol having a clay concentration of 5 to 15 wt% and a humic acid concentration of 5 to 15%.
A wt% humic acid solution is mixed at a mixing (weight) ratio of the clay component and the humic acid component of 8: 2 to 6: 4 to obtain a mixed sol having a pH of 4 to 8 1 x 10 2 of sol
Provided is a method for producing a clay-humic acid composite porous body, which comprises rapidly freezing at an average freezing rate of at least ml / sec and then drying without thawing.
【０００６】本発明者らは、前記した粘土ゾルを急速凍
結し、ついで融解することなく乾燥することにより得ら
れる粘土多孔体の強度向上を図るために、他の無機物
質、例えばカオリナイト、雲母、水ガラス、ロックウー
ル、ガラスファイバー等との複合化により実用強度を有
する多孔体の製造を試みたがこれもまた十分なものでは
なかった。本発明者らは、これらの研究により粘度と他
の無機物質との複合化では強度アップは難しく、また、
脆さが伴うということを知見し、更なる複合素材の研究
を、地球環境親和素材という観点より探索した。その結
果、生物が土中で腐敗分解した最終生成物であるフミン
酸（腐植酸）は、粘土と同様な土質成分であり、しかも
天然の土壌に容易に変換され、生態系の中に組み込まれ
る地球環境親和素材であることから、これを粘土に特定
量添加したところ、環境に親和的で緩衝性を備え、しか
も平均細孔径が小さく、圧縮強度に優れた粘度多孔体が
得られることを見出し、本発明に到達した。In order to improve the strength of the clay porous body obtained by rapidly freezing the above clay sol and then drying it without melting it, the present inventors have tried to improve the strength of other inorganic substances such as kaolinite and mica. Attempts were made to produce a porous body having practical strength by combining it with water glass, rock wool, glass fiber, etc., but this was also not sufficient. The inventors of the present invention have found that it is difficult to increase the strength by combining the viscosity with other inorganic substances, based on these studies.
Knowing that brittleness is involved, I searched for further research on composite materials from the viewpoint of materials that are friendly to the global environment. As a result, humic acid (humic acid), which is the final product of decay and decomposition of organisms in soil, is a soil component similar to clay, and is easily converted into natural soil and incorporated into ecosystems. Since it is a material compatible with the global environment, it was found that when a specific amount of this is added to clay, a viscous porous material that is environmentally friendly, has a buffering property, has a small average pore size, and has excellent compressive strength can be obtained. Has reached the present invention.
【０００７】本発明に用いられる粘土としては、たとえ
ば、モンモリロナイト、サポナイト、バイデライト、カ
オリナイト、アロフェン、セピオライト及びベントナイ
トなどの粘土、または、これらの粘土を合成した合成粘
土等が用いられる。また、本発明で用いるフミン酸は、
天然もしくは、ニトロフミン酸、フミン酸アンモニウ
ム、フミン酸ナトリウム等、人工的に抽出合成されたも
のであってもよい。Examples of the clay used in the present invention include clays such as montmorillonite, saponite, beidellite, kaolinite, allophane, sepiolite and bentonite, and synthetic clays obtained by synthesizing these clays. Further, humic acid used in the present invention is
It may be natural or artificially extracted and synthesized, such as nitrohumic acid, ammonium humate, or sodium humate.
【０００８】本発明の粘土−フミン酸複合多孔体を製造
するには、まず粘土ゾル及びフミン酸溶液を調整する。
粘土は膨潤能を持っているため予めゾル化しておかない
と継子となり不均一となる恐れがある。また、フミン酸
の場合も同様であり溶液化して混合したほうが分散性の
点からも均一に混合が可能になる。粘土ゾル及びフミン
酸溶液を調整する場合、溶媒としては水、アルコール、
水−アルコール混合溶媒などが使用できるが、アルコー
ル溶媒は濃度変化を起しやすく、また地球環境親和素材
という意味でも、コスト的にも水の使用が最も好まし
い。In order to produce the clay-humic acid composite porous material of the present invention, first, a clay sol and a humic acid solution are prepared.
Clay has a swelling ability, so if it is not made into a sol beforehand, it may become a step and become uneven. Further, the same applies to the case of humic acid, and it is possible to uniformly mix the humic acid when it is made into a solution and mixed in terms of dispersibility. When preparing a clay sol and humic acid solution, the solvent is water, alcohol,
Although a water-alcohol mixed solvent or the like can be used, it is most preferable to use water in terms of cost because the alcohol solvent easily causes a change in concentration and is also a material friendly to the global environment.
【０００９】つぎに、本発明では、得られた粘土ゾル及
びフミン酸溶液を混合し、該混合物を成形型に入れて形
成し、凍結させ、該凍結体を融解することなく乾燥させ
る。粘土ゾルの濃度は５〜１５ｗｔ％、好ましくは８〜
１２ｗｔ％である。濃度が５ｗｔ％未満の場合，多孔体
としての実用強度が得られず、また、１５ｗｔ％を越え
ると粘土性が高くなり、均一混練が難しくなる。フミン
酸溶液の濃度は、５〜１５ｗｔ％好ましくは７〜１２ｗ
ｔ％である。１５ｗｔ％を越えるフミン酸を使用した場
合には沈殿が生じ、混合の際、添加量を制御することが
困難となる。また、フミン酸溶液の濃度が５ｗｔ％未満
であると、圧縮強度が不充分となる。本発明における凍
結乾燥は、１×１０2ｍｌ／秒以上の平均凍結速度で急
速に凍結することが必要である。このようにすると、ミ
クロンオーダーの微細空孔の多孔体が得られる。１×１
０2ｍｌ／秒未満の場合には、多孔体の空孔が大きくな
りすぎ、強度が極めて小さくなるため、好ましくない。Next, in the present invention, the obtained clay sol and humic acid solution are mixed, the mixture is put in a mold to form, frozen, and the frozen body is dried without being thawed. The concentration of clay sol is 5 to 15 wt%, preferably 8 to
12 wt%. When the concentration is less than 5 wt%, practical strength as a porous body cannot be obtained, and when it exceeds 15 wt%, the clay property becomes high and uniform kneading becomes difficult. The concentration of the humic acid solution is 5 to 15 wt%, preferably 7 to 12 w
t%. When humic acid exceeding 15 wt% is used, precipitation occurs, and it becomes difficult to control the addition amount during mixing. Further, if the concentration of the humic acid solution is less than 5 wt%, the compressive strength will be insufficient. Freeze-drying in the present invention requires rapid freezing at an average freezing rate of 1 × 10 2 ml / sec or more. By doing so, a porous body having microscopic pores of micron order can be obtained. 1 x 1
If it is less than 0 2 ml / sec, the pores of the porous body become too large and the strength becomes extremely small, which is not preferable.
【００１０】本発明においては、粘土ゾル及びフミン酸
溶液の混合ゾルのｐＨを４〜８の調整する。このような
混合ゾルから作られた多孔体は、フミン酸が粘土中に細
かく均一に分散し、粘土単体で作成した多孔体より更に
細かい微細空孔が形成され、緩衝性に富む多孔体が得ら
れる。ｐＨが６未満であった場合、粘土：フミン酸組成
比により異なるが、ある程度の強度を持つ多孔体は得ら
れるものの、圧縮強度が実用強度までに達しにくくな
り、更にｐＨが４未満の場合、酸性領域まで達すると粘
土鉱物中の金属イオン、及びシリカが溶出し、粘土の構
造が破壊される。またフミン酸はこのような酸性溶液中
では球状に凝集し粘土中に巨大粒子として分散し、粘土
の構造破壊とフミン酸の均一分散の悪化により得られる
多孔体は空孔が大きくなり、圧縮強度等の実用強度が得
られなくなる。一方、ｐＨが８を越え、アルカリ性領域
下では、粘土構造中のシリカが溶出し、構造が破壊され
て得られる多孔体の圧縮強度等の実用強度が得られなく
なる。In the present invention, the pH of the mixed sol of the clay sol and the humic acid solution is adjusted to 4-8. In the porous body made from such mixed sol, humic acid is finely and uniformly dispersed in clay, and finer pores are formed than in the porous body made of clay alone, so that a porous body having a high buffering property is obtained. To be When the pH is less than 6, although it depends on the composition ratio of clay: humic acid, a porous material having a certain level of strength can be obtained, but it is difficult to reach the practical strength of the compressive strength, and when the pH is less than 4, When it reaches the acidic region, the metal ions in the clay mineral and silica are eluted and the structure of the clay is destroyed. Humic acid aggregates spherically in such an acidic solution and disperses as huge particles in clay, and the porous body obtained by the structural destruction of clay and the deterioration of uniform dispersion of humic acid has large pores and compressive strength. It becomes impossible to obtain practical strength such as. On the other hand, when the pH exceeds 8 and in the alkaline range, silica in the clay structure is eluted and the structure is destroyed, so that the practical strength such as the compressive strength cannot be obtained.
【００１１】ｐＨ調整には、通常、塩酸及び水酸化ナト
リウム水溶液が用いられるが、特にこれらに制限される
ものではなく、硫酸、硝酸、酢酸、燐酸、過塩素酸、硼
酸、水酸化カリウム、水酸化アルミニウム、及び水酸化
カルシウム等を使用してもよい。尚、上記ｐＨ調整は、
粘土成分とフミン酸成分の組成、混合比によっては不要
の場合もある。For the pH adjustment, hydrochloric acid and an aqueous solution of sodium hydroxide are usually used, but the pH is not particularly limited to these, and sulfuric acid, nitric acid, acetic acid, phosphoric acid, perchloric acid, boric acid, potassium hydroxide, water are used. You may use aluminum oxide, calcium hydroxide, etc. In addition, the above pH adjustment is
It may not be necessary depending on the composition and mixing ratio of the clay component and the humic acid component.
【００１２】また、本発明においては、粘土成分とフミ
ン酸成分の混合割合を重量比で８：２〜６：４、好まし
くは７：３〜６：４に混合することが必要である。混合
割合でフミン酸成分が２０ｗｔ％未満の場合、フミン酸
添加による空孔の微細化、つまり強度アップの効果が薄
く、圧縮強度等が実用強度に達しない。一方フミン酸成
分が４０ｗｔ％を越える場合、粘土成分が少なすぎて、
多孔体の圧縮強度等が低下する。Further, in the present invention, it is necessary to mix the clay component and the humic acid component in a weight ratio of 8: 2 to 6: 4, preferably 7: 3 to 6: 4. If the humic acid component is less than 20 wt% in the mixing ratio, the effect of refining the pores by adding humic acid, that is, the effect of increasing the strength is small, and the compressive strength or the like does not reach the practical strength. On the other hand, when the humic acid component exceeds 40 wt%, the clay component is too small,
The compressive strength of the porous body is reduced.
【００１３】上述の通り、本発明において、粘土とフミ
ン酸との混合比率、並びに混合ゾルのｐＨを変えること
により、多孔体の空孔の大きさを変え、機械的強度、特
に圧縮強度を３．００ｋｇｆ／ｃｍ2以上、特に３．０
０〜３．８０ｋｇｆ／ｃｍ2に制御することができる。
本発明の多孔体を得る場合、原料混合物はゾル状である
と、形状は限定されず成形型に容易に充填し任意形状に
成形することができる。また凍結乾燥の際、水／氷の相
転移に伴う膨張の為、内圧を生じ、微細なガラス状の成
型が可能であり、収縮がなく、寸法精度の良いものが得
られる。本発明の多孔体は、乾燥後、そのまま製品とし
て使用でき、前記したように形状は板状体のほか、ブロ
ック体や柱状体、筒状体等の任意の形状とすることがで
きる。As described above, in the present invention, by changing the mixing ratio of clay and humic acid and the pH of the mixed sol, the size of the pores of the porous body is changed, and the mechanical strength, particularly the compressive strength, is increased to 3 0.000 kgf / cm 2 or more, especially 3.0
It can be controlled to 0 to 3.80 kgf / cm 2 .
When the raw material mixture is in the form of a sol when obtaining the porous body of the present invention, the shape is not limited, and it can be easily filled in a molding die and molded into an arbitrary shape. Further, during freeze-drying, expansion occurs due to the phase transition of water / ice, so that internal pressure is generated, fine glass-like molding is possible, shrinkage does not occur, and a product with good dimensional accuracy can be obtained. The porous body of the present invention can be used as a product as it is after being dried, and as described above, the shape can be an arbitrary shape such as a block body, a columnar body, or a tubular body in addition to the plate body.
【００１４】[0014]
【実施例】次に本発明を実施例により更に詳細に説明す
る。 実施例１〜６、比較例１〜１７ 山形県左沢産の天然ベントナイトとを水簸し、２μｍ以
下の鉱物のみを集めモンモリロナイト成分を濃集し、Ｎ
ａＣｌ水溶液を用いてモンモリロナイトの層間イオンを
Ｎａ＋に置換し、水洗した後乾燥して原料とした。この
原料と塩酸水溶液又は水酸化ナトリウム水溶液を使用し
て適宜にｐＨを調整し、計量混合して、固：液比が１：
９の粘土ゾルを作り一昼夜放置して熟成した。フミン酸
は市販されているもの（フミン酸アンモニウム；ＣＨＡ
−０７：テルナイト社製）を使用し、塩酸水溶液又は水
酸化ナトリウム水溶液により同様にｐＨを調整し、固：
液比を１：９に計量しての水溶液を作成し、一昼夜放置
して熟成した。次いで粘土ゾル／フミン酸水溶液の比率
を１００：０、９０：１０、８０：２０、７０：３０、
６０：４０、５０：５０、及び０：１００に調整した。
ただし、粘土ゾル：フミン酸水溶液の比率が１００：
０、及び０：１００は、それぞれ粘土ゾル、フミン酸水
溶液だけである。これらは厳密には混合ゾルではない
が、混合ゾルと同様に扱った。これらの混合ゾルのｐＨ
を表１記載のように調整し、ついで得られた混合ゾルを
内径２０ｍｍφ、高さ３０ｍｍのステンレス製の筒状容
器に入れ、容器ごと液体窒素に浸して、１×１０2ｍｌ
／秒以上の平均凍結速度で急速に凍結し、その後凍結体
を真空乾燥して、微細空孔を有する多孔体を作成した。
得られた多孔体の圧縮強度及び細孔径を測定し、評価を
行った。その結果を表−１に示す。併せて市販のポリス
チレンフォーム（（株）ＪＳＰ社製 ミラフォームＭＩ
Ｆ）についても同様に圧縮強度を測定した。なお、作製
したすべての多孔体の密度は０．１ｇ／ｃｍ3とした。EXAMPLES The present invention will now be described in more detail with reference to Examples. Examples 1 to 6, Comparative Examples 1 to 17 Natural bentonite from Sazawa, Yamagata Prefecture was elutriated, and only minerals of 2 μm or less were collected to concentrate the montmorillonite component.
The interlayer ions of montmorillonite were replaced with Na + using an aCl aqueous solution, washed with water, and then dried to obtain a raw material. The pH is adjusted appropriately using this raw material and an aqueous solution of hydrochloric acid or an aqueous solution of sodium hydroxide, and the mixture is weighed and mixed to give a solid: liquid ratio of 1:
Clay sol No. 9 was prepared and left for one day and aged for aging. Humic acid is commercially available (ammonium humate; CHA
-07: manufactured by Ternite Co., Ltd.), the pH is similarly adjusted with an aqueous hydrochloric acid solution or an aqueous sodium hydroxide solution, and solid:
The liquid ratio was measured to be 1: 9 to prepare an aqueous solution, which was left to stand overnight for aging. Next, the ratio of clay sol / humic acid aqueous solution is 100: 0, 90:10, 80:20, 70:30,
Adjusted to 60:40, 50:50, and 0: 100.
However, the ratio of clay sol: humic acid aqueous solution is 100:
0 and 0: 100 are only clay sol and humic acid aqueous solution, respectively. Although these are not strictly mixed sols, they were treated similarly to mixed sols. PH of these mixed sols
Was adjusted as shown in Table 1, and then the obtained mixed sol was placed in a stainless steel cylindrical container having an inner diameter of 20 mmφ and a height of 30 mm, and the whole container was immersed in liquid nitrogen to obtain 1 × 10 2 ml.
The sample was rapidly frozen at an average freezing rate of not less than 1 sec / second, and then the frozen body was vacuum-dried to form a porous body having fine pores.
The compressive strength and pore size of the obtained porous body were measured and evaluated. The results are shown in Table-1. In addition, commercially available polystyrene foam (Mirafoam MI manufactured by JSP Corp.)
The compressive strength of F) was measured in the same manner. The density of all the prepared porous bodies was 0.1 g / cm 3 .
【００１５】本実施例で用いた測定方法を以下に示す。 （圧縮強度） ・径２０ｍｍφ×高さ３０ｍｍの円柱状の多孔体を０．
５ｍｍ／ｍｉｎの試験速度で高さ方向に１０％圧縮した
時の圧縮力から圧縮強度を算出した。（圧縮試験装置：
インストロン ＭＯＤＥＬ−１１２３） （平均細孔径） ・平均細孔径は水銀圧入式の水銀ポロシメーター（ＣＡ
ＲＬＯＥＲＢＡ Ｐｏｌｏｓｉｍｅｔｅｒ Ｓｅｒｉｅ
ｓ２００）で測定した。 （多孔体評価） ◎ 優：圧縮強度が３．５０ｋｇｆ／ｃｍ2を超え、機
械的強度に優れると共に外観に優れる。 ○ 良：圧縮強度が３．００〜３．５０ｋｇｆ／ｃｍ2
であり、機械的強度に優れると共に外観に優れる。 × 悪：圧縮強度が３．００ｋｇｆ／ｃｍ2未満であ
り、機械的強度に劣り、脆く、また外観が不良である。The measuring method used in this example is shown below. (Compressive strength) ・ A cylindrical porous body having a diameter of 20 mmφ and a height of 30 mm was set to 0.
The compressive strength was calculated from the compressive force when 10% was compressed in the height direction at a test speed of 5 mm / min. (Compression tester:
Instron MODEL-1123) (Average pore size) -The average pore size is the mercury porosimetry mercury porosimeter (CA).
RLOERBA Porosimeter Series
s200). (Evaluation of Porous Material) Excellent: Compressive strength exceeds 3.50 kgf / cm 2 , excellent in mechanical strength and appearance. Good: Compressive strength of 3.00 to 3.50 kgf / cm 2
And has excellent mechanical strength and appearance. × Poor: Compressive strength is less than 3.00 kgf / cm 2 , mechanical strength is poor, brittle, and appearance is poor.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【発明の効果】本発明において得られる多孔体は、粘土
とフミン酸という土質成分からなるものであるため、回
収再利用が可能であり、廃棄に際しても天然の土壌に容
易に変換され、生態系の中に組み込まれる非常に新しい
地球環境親和素材であり、緩衝材、断熱材、吸音材等と
して有利に用いられる。本発明の多孔体の製造方法は、
凍結乾燥の際、水／氷の相転移に伴う膨張の為、内圧を
生じ、微細なガラス状の成型が可能であり、また、収縮
がなく、寸法精度の良い多孔体が得られる。このため、
乾燥後すぐに製品として使用することができるという利
点を有する。また、粘土とフミン酸との混合比率、並び
に混合ゾルのｐＨを変えることにより、多孔体の細孔径
の制御並びに、機械的強度、特に圧縮強度を制御するこ
とができるという長所を有する。Industrial Applicability The porous material obtained in the present invention is composed of clay and humic acid, which are soil components. Therefore, it can be recovered and reused, and can be easily converted to natural soil even when it is discarded. It is a very new material compatible with the global environment that is incorporated into the product, and is advantageously used as a cushioning material, heat insulating material, sound absorbing material, etc. The method for producing a porous body of the present invention is
During freeze-drying, expansion occurs due to the phase transition of water / ice, so that internal pressure is generated, fine glass-like molding is possible, and there is no shrinkage, and a porous body with good dimensional accuracy can be obtained. For this reason,
It has the advantage that it can be used as a product immediately after drying. Further, by changing the mixing ratio of clay and humic acid and the pH of the mixed sol, it is possible to control the pore size of the porous body and the mechanical strength, particularly the compressive strength.
Claims (2)
細孔径が０．８μｍ〜２．０μｍであり、圧縮強度が
３．００ｋｇｆ／ｃｍ2以上であることを特徴とする粘
土−フミン酸複合多孔体。1. A clay-humic acid composite having a humic acid component of 20 to 40 wt%, an average pore diameter of 0.8 μm to 2.0 μm, and a compressive strength of 3.00 kgf / cm 2 or more. Porous body.
フミン酸濃度が５〜１５ｗｔ％のフミン酸溶液とを、粘
土成分とフミン酸成分との混合（重量）比が、８：２〜
６：４の割合で混合して混合ゾルを得、ｐＨが４〜８の
該混合ゾルを１×１０2ｍｌ／秒以上の平均凍結速度で
急速凍結し、次いで融解することなく乾燥することを特
徴とする粘土−フミン酸複合多孔体の製造方法。2. A clay sol having a clay concentration of 5 to 15 wt% and a humic acid solution having a humic acid concentration of 5 to 15 wt% have a mixing (weight) ratio of the clay component and the humic acid component of 8: 2.
A mixed sol is obtained by mixing in a ratio of 6: 4, and the mixed sol having a pH of 4 to 8 is rapidly frozen at an average freezing rate of 1 × 10 2 ml / sec or more, and then dried without thawing. A method for producing a clay-humic acid composite porous body characterized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7103111A JP2691696B2 (en) | 1995-04-04 | 1995-04-04 | Clay-humic acid composite porous body and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7103111A JP2691696B2 (en) | 1995-04-04 | 1995-04-04 | Clay-humic acid composite porous body and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08277174A true JPH08277174A (en) | 1996-10-22 |
| JP2691696B2 JP2691696B2 (en) | 1997-12-17 |
Family
ID=14345505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7103111A Expired - Lifetime JP2691696B2 (en) | 1995-04-04 | 1995-04-04 | Clay-humic acid composite porous body and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2691696B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245549A2 (en) | 2001-03-28 | 2002-10-02 | Asahi Glass Company Ltd. | Process for preparing silicate porous product |
| WO2008084530A1 (en) | 2007-01-10 | 2008-07-17 | Shiseido Company, Ltd. | Dispersion solution of humic substance |
| CN104474787A (en) * | 2014-12-08 | 2015-04-01 | 西安建筑科技大学 | Filter material for sewage treatment and preparation method for filter material for sewage treatment |
| WO2020178538A1 (en) * | 2019-03-06 | 2020-09-10 | Materr'up | Method for selecting the composition of a construction material comprising an excavated clay soil, method and system for preparing such a construction material |
| FR3128954A1 (en) * | 2022-11-07 | 2023-05-12 | Materrup | Method for selecting the composition of a building material comprising an excavated clay soil, method and system for preparing such a building material |
-
1995
- 1995-04-04 JP JP7103111A patent/JP2691696B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245549A2 (en) | 2001-03-28 | 2002-10-02 | Asahi Glass Company Ltd. | Process for preparing silicate porous product |
| WO2008084530A1 (en) | 2007-01-10 | 2008-07-17 | Shiseido Company, Ltd. | Dispersion solution of humic substance |
| CN104474787A (en) * | 2014-12-08 | 2015-04-01 | 西安建筑科技大学 | Filter material for sewage treatment and preparation method for filter material for sewage treatment |
| WO2020178538A1 (en) * | 2019-03-06 | 2020-09-10 | Materr'up | Method for selecting the composition of a construction material comprising an excavated clay soil, method and system for preparing such a construction material |
| FR3093513A1 (en) * | 2019-03-06 | 2020-09-11 | Materr'up | Method of selecting the composition of a building material comprising excavated clay soil, method and system for preparing such a building material |
| US11401215B2 (en) | 2019-03-06 | 2022-08-02 | Materr'up | Method for selecting the composition of a construction material comprising an excavated clay soil, method and system for preparing such a construction material |
| US11827573B2 (en) | 2019-03-06 | 2023-11-28 | Materrup | Method for selecting the composition of a construction material comprising an excavated clay soil, method and system for preparing such a construction material |
| FR3128954A1 (en) * | 2022-11-07 | 2023-05-12 | Materrup | Method for selecting the composition of a building material comprising an excavated clay soil, method and system for preparing such a building material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2691696B2 (en) | 1997-12-17 |
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