WO2003041837A1 - Water-floating zeolite composites - Google Patents

Water-floating zeolite composites Download PDF

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Publication number
WO2003041837A1
WO2003041837A1 PCT/JP2002/011986 JP0211986W WO03041837A1 WO 2003041837 A1 WO2003041837 A1 WO 2003041837A1 JP 0211986 W JP0211986 W JP 0211986W WO 03041837 A1 WO03041837 A1 WO 03041837A1
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WIPO (PCT)
Prior art keywords
zeolite
water
floating
carrier
support
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PCT/JP2002/011986
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French (fr)
Japanese (ja)
Inventor
Hirotsugu Aoki
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Japan System Products Co., Ltd.
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Publication of WO2003041837A1 publication Critical patent/WO2003041837A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/24—Feed or discharge mechanisms for settling tanks
    • B01D21/2433—Discharge mechanisms for floating particles
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a zeolite composite, particularly a water-floating zeolite composite floating in water, and a method for producing the same.
  • the physical treatment method is a method of physically separating solid and liquid, and the sedimentation separation is the main stream of separation operation in wastewater treatment, and is the simplest method among physical treatment methods.
  • the sedimentation separation method includes the natural sedimentation method and the coagulation sedimentation method.
  • Coagulation sedimentation is a method of adding fine particles in water, which cannot be sedimented within economic time due to natural sedimentation and agitating, generates flocs and binds to each other, grows into large aggregates, and increases sedimentation It is a way to make it.
  • As the flocculant various water-soluble inorganic and organic substances are used. Inorganic substances are generally low-molecular-weight salts, and the action of aluminum salts and iron salts in the vicinity of neutrality is the action of low-polymerized substances.
  • the main component of organic matter is water-soluble polymer substances.
  • the process of coagulation and sedimentation of water is as follows: i) coagulation process in which coagulant coagulates suspended material to form micro flocs; ii) micro flocs generated in coagulation process collide and come into contact with each other Iii) A sedimentation separation process that separates the large flocs generated during the floc formation process from the clarified water. These three processes are generally performed using separate devices. Therefore, it takes a long time to separate and concentrate the solid particles in the suspension by coagulation and sedimentation of water.
  • a rapid coagulation and sedimentation device is one of those three processes that can be performed by one device.
  • the sedimentation / separation speed of the rapid coagulation sedimentation apparatus varies depending on the quality of the raw water, but it is usually designed to be 2-3 m / hr, and the residence time is to be 50-70 minutes.
  • sedimentation separation is the mainstream of separation operation in wastewater treatment, rapid separation is performed solely by improving the coagulation and sedimentation treatment mechanism, and the sedimentation separation speed is limited, and the coagulation function of the flocculant is limited. It has not been improved to rapidly form large-grained flocks. Disclosure of the invention
  • the present invention solves the above-mentioned problems of the prior art, and is an underwater buoyant zeolite composite having the following constitution.
  • a water-floating zeolite composite comprising zeolite and a support having an apparent density of 0.7 to 1.2, preferably 0.9 to 1.0, supporting the zeolite. .
  • a granular material comprising zeolite powder and a granular carrier having an apparent density of 0.7 to 1.2, preferably ⁇ 9 to 1.0, which supports them on the surface. Water-floating zeolite composite.
  • a plate-like water characterized by comprising a zeolite powder and a plate-like support having an apparent density of 0.7 to 1.2, and preferably 0.9 to 1.0, which support them.
  • Floating zeolite composite Floating zeolite composite.
  • a hollow-body water-floating zeolite composite comprising: a hollow-body support of 0.9 to 1.0.
  • a fibrous material characterized by comprising a zeolite powder and a fibrous apparent density supporting the zeolite powder of 0.7 to 1.2, preferably 0.9 to 1.0. Water-floating zeolite composite.
  • Mesh-like water characterized by comprising a zeolite powder and a mesh-like apparent density supporting the zeolite powder of 0.7 to 1.2, preferably 0.9 to 1.0. Floating zeolite composite.
  • Tape-like water characterized by comprising zeolite powder and a tape-like apparent density supporting them of 0.7 to 1.2, preferably 0.9 to 1.0 Floating zeolite composite.
  • Honeycomb-shaped comprising a zeolite powder and a carrier having a honeycomb-shaped apparent density of 0.7 to 1.2, and preferably 0.9 to 1.0. Water-floating zeolite composite.
  • the zeolite powder or the carrier is an adsorbent.
  • FIG. 1 to 5 show a cross-sectional view and an external view of a zeolite composite in water of various shapes
  • FIG. 1 shows a zeolite powder layer 1 adhered to the surface of a hollow support 2.
  • Fig. 3 shows a zeolite powder layer 1 attached to the surface of a fibrous carrier 3
  • Fig. 3 shows a zeolite powder layer 1 attached to the surface of a mesh-shaped carrier 4
  • Fig. 4 shows a tape-shaped carrier 5
  • FIG. 5 shows a structure in which the zeolite powder layer 1 is adhered
  • FIG. 5 shows a structure in which the zeolite powder layer 1 is sintered and adhered to the inner surface of the honeycomb-shaped carrier 6.
  • the zeolite composite of the present invention floats without immediately settling in water (water to be treated), and therefore has an apparent density of 0.7 to 1.2, preferably 0.9 to 1
  • the structure is such that it is carried on a carrier of.
  • the specific gravity (density) of the water to be treated is 1.0 in the case of only water, but may be 1.1 to 1.2 in the case of a suspension containing a muddy substance.
  • the concentration may be 1.0 or less, so a carrier having an apparent density corresponding to these various specific gravity liquids is used.
  • High purity Zeoraito is a pure 9 9 wt% or more hydrated aluminosilicate, ⁇ ratio, i.e. (S I_ ⁇ 2 and A 1 2 0 3 composition by weight ratio) XI. 7, the 3 Zeolite A, zeolite P (phillipsite), zeolite X (fojasite), zeolite Y (fojasite) and zeolite corresponding to hydroxysodalite.
  • the cation exchange capacity is 400-600.111 0 1 (+) kg- 1 and all correspond to the theoretical values of the structure of the zeolite.
  • Zeolite is obtained by artificially converting a composition containing an amorphous aluminum silicate salt composed of an inorganic component containing silicic acid and aluminum by alkali treatment, and its main component is philipsite, mordenite, and fauja. Site, zeolite, hydroxysodalite, etc., may contain small amounts of other components. In addition, organic substances, iron, other impurities, and intermediate products up to zeolite coexist as a part other than zeolite, that is, as a non-zeolite component.
  • the substance containing silicic acid and aluminum is added with 0.1 to 5.ON alkaline water. After adding the solution and heat-treating it at 60 to 280 ° C, the solution part is separated. Zeolite can be produced by treating the insoluble residue at this time with alkali.
  • the substances containing silicic acid and aluminum as raw materials for zeolite production include those containing silicic acid and aluminum as aluminum silicate salts.
  • Examples include ash, incinerated ash of combustible waste, incinerated ash of sludge, and incinerated ash when burning solid waste fuel called RDF as a heat source.
  • the above-mentioned underwater floating 'I' raw zeolite composite can be used to treat polluted wastewater, such as industrial wastewater and municipal wastewater, for a long period of time by agitation to bring it into contact with the wastewater in a suspended state, and as a result, The pollutants in the wastewater can be efficiently removed by contacting the zeolite.
  • the shape of the zeolite carrier may be a granular body, a plate-like body, a hollow body, a fiber body, It may be a mesh, a tape, a honeycomb, or the like.
  • Fig. 1 shows a zeolite powder layer 1 attached to the surface of a hollow carrier 2;
  • Fig. 2 shows a zeolite powder layer 1 attached to the surface of a fibrous carrier 3;
  • Fig. 5 shows a honeycomb-shaped carrier 6 with an inner surface of zeolite powder.
  • the powder layer 1 is formed by sintering and adhering, respectively.
  • 1 is a zeolite powder layer
  • 2 is a hollow carrier
  • 3 is a fibrous carrier
  • 4 is a mesh carrier.
  • 5 is a tape-shaped carrier
  • 6 is a honeycomb-shaped carrier.
  • the zeolite powder or carrier may carry a catalyst, a coagulation aid, an adsorbent, a decolorizing agent, a bactericide, an antibacterial agent, an organic substance-degrading microorganism, an enzyme, and the like.
  • the carrier may be a porous ceramic or a porous plastic.
  • the zeolite or the carrier may support an aggregating agent, or may be a zeolite crystalloid aggregating agent.
  • Specific examples of the carrier include volcanic ejecta having a large number of single holes, pearlite obtained by heating and expanding obsidian and perlite, or hollow glass particles, and foamed resin such as polyurethane foam and styrofoam. Is raised.
  • the carrier may carry an antibacterial agent such as activated carbon or silver zeolite, an organic substance-decomposing microorganism that decomposes organic pollutants as a nutrient source, or an enzyme for producing alcoholic beverages.
  • an antibacterial agent such as activated carbon or silver zeolite
  • an organic substance-decomposing microorganism that decomposes organic pollutants as a nutrient source
  • an enzyme for producing alcoholic beverages an enzyme for producing alcoholic beverages.
  • a preferable configuration example of the present invention is a water-floating zeolite composite in which a carrier supports an organic substance-degrading microorganism, and a zeolite on the surface thereof supports a flocculant. When it is put into urban wastewater, industrial wastewater, etc., and stirred, the suspended substance is first flocculated and settled by flocculant, for example, a sulfate band, polychlorinated aluminum, or polyacrylamide-based flocculant.
  • the water becomes clarified transparent water, and then the organic pollutants dissolved in the clear water are consumed and decomposed by the organically degrading microorganisms on the carrier. In addition, it may be necessary to perform air ration during the treatment of the microorganisms.
  • the water to be treated using the water-floating zeolite composite of the present invention includes, in addition to the above, gravel wastewater, wastewater containing red soil, sludge, tunnel construction wastewater, activated sludge water, household wastewater, and the like.
  • zeolite composite of this invention since it can float in water without immediately settling out, it can be contacted with various wastewater to be treated for a long time, and as a result, zeolite can sufficiently treat the water to be treated. Can be efficiently processed.

Abstract

It is intended to provide water-floating zeolite composites which do not immediately sediment but float in water and thus can remain in contact with various wastewaters or the like to be treated over a prolonged period of time. A water-floating zeolite composite composed of a zeolite powder layer (1) and a support which holds it and has an apparent density of from 0.9 to 1.0. The support may be in the form of grains, a hollow article (2), a fiber, a mesh, a tape, a honeycomb, etc. It may further hold a substance having a catalytic action, an aggregation aid, an adsorbent, etc. As a preferred example, a constitution wherein the support holds a microorganism capable of degrading organic matters and zeolite provided on the surface of the support holds an aggregate reagent may be cited. When such a composite is poured into town sewage, plant wastewater or the like and stirred therein, suspended matters first aggregate together to form flocks and sediment to give clarified transparent supernatant water. Next, organic contaminants dissolved in the transparent water are consumed and degraded by the microorganism.

Description

明 細 書 水中浮遊性ゼォライト複合物 発明の技術分野  Description Water-floating zeolite composite Technical field of the invention
本発明は、 ゼォライト複合物、 特に水中において浮遊する水中浮遊性ゼォライ ト複合物及びその製造方法に関するものである。 背景技術  TECHNICAL FIELD The present invention relates to a zeolite composite, particularly a water-floating zeolite composite floating in water, and a method for producing the same. Background art
産業の発達に伴う産業廃水の増大、 都市への人口の集中による生活廃水の増大 等により、 河川、 湖沼、 海洋等の自然環境の汚染が深刻な状態となっている。 各種廃水の処理は、 種々の処理法及ぴ処理装置によって行われ、 1 ) 物理的処 理法 （スクリーニング、 沈砂、 沈澱、 濾過、 浮上など） 、 2 ) 化学的処理法 （中 和、 酸化と還元、 凝集処理など） 、 3 ) 生物化学的処理方法 （活性汚泥法、 散水 瀘床法、 メタン発酵法） などがあるが、 処理すべき物質、 廃水の水質や排出量が きわめて多様であるため、 単純な処理法及ぴ装置では処理できない問題がある。 上記のうち、 物理的処理法は、 要するに固液を物理的に分離する方法であり、 沈降分離は、 廃水処理における分離操作の主流をなしており、 物理的処理方法の 中でも最も簡単な方法である。 沈降分離法には、 自然沈殿法と、 凝集沈殿法とが める。 凝集沈殿は、 自然沈殿で経済時間内で沈降できないような水中の微粒子を凝集 剤を添加して撹拌し、 フロックを生じさせて互いに結合し、 大粒の凝塊に成長さ せ、 沈降性を増加させる方法である。 凝集剤には水溶性の各種の無機物、 有機物 が使用され、 無機物は一般に低分子の塩で、 中性付近でのアルミニウム塩や鉄塩 の作用は低度の重合物の作用である。 有機物の主体を占めるのは、 水溶性高分子 物質である。  The pollution of the natural environment such as rivers, lakes, marshes, and oceans has become serious due to the increase in industrial wastewater due to the development of industry and the increase in domestic wastewater due to the concentration of population in cities. Various wastewater treatments are performed by various treatment methods and treatment equipment, 1) physical treatment methods (screening, sedimentation, sedimentation, filtration, flotation, etc.), 2) chemical treatment methods (neutralization, oxidation and reduction) , Coagulation treatment, etc.), 3) Biochemical treatment methods (activated sludge method, sprinkling filter method, methane fermentation method), etc., but the substances to be treated, the quality of wastewater and the amount of discharge are extremely diverse, There is a problem that it cannot be processed with a simple processing method and a simple apparatus. Among the above, the physical treatment method is a method of physically separating solid and liquid, and the sedimentation separation is the main stream of separation operation in wastewater treatment, and is the simplest method among physical treatment methods. is there. The sedimentation separation method includes the natural sedimentation method and the coagulation sedimentation method. Coagulation sedimentation is a method of adding fine particles in water, which cannot be sedimented within economic time due to natural sedimentation and agitating, generates flocs and binds to each other, grows into large aggregates, and increases sedimentation It is a way to make it. As the flocculant, various water-soluble inorganic and organic substances are used. Inorganic substances are generally low-molecular-weight salts, and the action of aluminum salts and iron salts in the vicinity of neutrality is the action of low-polymerized substances. The main component of organic matter is water-soluble polymer substances.
水の凝集沈殿処理の過程は、 i ) 凝集剤が懸濁物質を凝集し、 微小フロックを 生成する凝集過程、 i i ) 凝集過程で生成した微小フロックが相互に衝突接触し て次第に大きなフロックを形成するフロック形成過程、 i i i) フロック形成過 程で生成した大きなフロックと清澄水とを分離する沈降分離過程からなり、 以上 の 3つの過程の処理は、 一般にそれぞれ別個の装置で行われるため、 水の凝集沈 降処理によって懸濁液中の固体粒子群の分離濃縮には長時間を必要とする。 この 3つの過程を一つの装置で行うものとして急速凝集沈殿装置があり、 その —つとして、 スラリー循環型ではすでに生成している高濃度のスラリーを凝集及 びフロック形成部分へ循環し、 微小フロックの大型フロックへのフロック形成を 促進して沈降分離しうる程度の大きさのフロックまでに成長させる機能をもつた ものである。 急速凝集沈殿装置の沈降分離速度は、 その原水の水質によって異な るが、 普通 2〜3m/h r、 滞留時間は 50〜 70分の範囲で設計される。 沈降分離は、 廃水処理における分離操作の主流をなしているものの、 その急速 分離は専ら凝集沈殿処理メカニズムを改善することによって行われており、 沈降 分離速度には限界があり、 凝集剤の凝集機能そのものを改善して急速に大粒のフ 口ックを形成させることはなされていなかった。 発明の開示 The process of coagulation and sedimentation of water is as follows: i) coagulation process in which coagulant coagulates suspended material to form micro flocs; ii) micro flocs generated in coagulation process collide and come into contact with each other Iii) A sedimentation separation process that separates the large flocs generated during the floc formation process from the clarified water.These three processes are generally performed using separate devices. Therefore, it takes a long time to separate and concentrate the solid particles in the suspension by coagulation and sedimentation of water. A rapid coagulation and sedimentation device is one of those three processes that can be performed by one device. One of them is the slurry circulation type, which circulates the already generated high-concentration slurry to the coagulation and floc formation part, and then generates fine floc. It has the function of promoting the formation of flocs on large flocs and growing them into flocs of a size large enough to settle and separate. The sedimentation / separation speed of the rapid coagulation sedimentation apparatus varies depending on the quality of the raw water, but it is usually designed to be 2-3 m / hr, and the residence time is to be 50-70 minutes. Although sedimentation separation is the mainstream of separation operation in wastewater treatment, rapid separation is performed solely by improving the coagulation and sedimentation treatment mechanism, and the sedimentation separation speed is limited, and the coagulation function of the flocculant is limited. It has not been improved to rapidly form large-grained flocks. Disclosure of the invention
本発明は、 上記従来技術の問題点を解決するもので、 下記構成の水中浮遊性ゼ ォライト複合物である。  The present invention solves the above-mentioned problems of the prior art, and is an underwater buoyant zeolite composite having the following constitution.
(1) ゼォライトとそれを担持する見掛け密度 0. .7〜1. 2好ましくは 0. 9 〜1. 0の担持体とより構成されてなることを特徴とする水中浮遊性ゼォライト 複合物。 .  (1) A water-floating zeolite composite comprising zeolite and a support having an apparent density of 0.7 to 1.2, preferably 0.9 to 1.0, supporting the zeolite. .
(2) ゼォライト粉末とそれらを表面に担持する見掛け密度 0. 7〜1. 2好ま しくは◦. 9〜1. 0の粒状の担持体とより構成されてなることを特徴とする粒 状の水中浮遊性ゼォライト複合物。  (2) A granular material comprising zeolite powder and a granular carrier having an apparent density of 0.7 to 1.2, preferably ◦ 9 to 1.0, which supports them on the surface. Water-floating zeolite composite.
(3) ゼォライト粉末とそれらを担持する見掛け密度 0. 7〜1. 2好ましくは 0. 9〜1. 0の板状の担持体とより構成されてなることを特徴とする板状の水 中浮遊性ゼォライト複合物。  (3) A plate-like water characterized by comprising a zeolite powder and a plate-like support having an apparent density of 0.7 to 1.2, and preferably 0.9 to 1.0, which support them. Floating zeolite composite.
(4) ゼォライト粉末とそれらを担持する見掛け密度 0. 7〜1. 2好ましくは 0. 9〜1. 0の中空体状の担持体とより構成されてなることを特徴とする中空 体状の水中浮遊性ゼォライト複合物。 (4) Zeolite powder and apparent density supporting them 0.7 to 1.2, preferably A hollow-body water-floating zeolite composite, comprising: a hollow-body support of 0.9 to 1.0.
(5) ゼォライト粉末とそれらを担持する繊維状の見掛け密度 0. 7〜1. 2好 ましくは 0. 9〜1. 0の担持体とより構成されてなることを特徴とする繊維状 の水中浮遊性ゼォライト複合物。  (5) A fibrous material characterized by comprising a zeolite powder and a fibrous apparent density supporting the zeolite powder of 0.7 to 1.2, preferably 0.9 to 1.0. Water-floating zeolite composite.
(6) ゼォライト粉末とそれらを担持するメッシュ状の見掛け密度 0. 7〜1. 2好ましくは 0. 9〜1. 0の担持体とより構成されてなることを特徴とするメ ッシュ状の水中浮遊性ゼォライト複合物。  (6) Mesh-like water characterized by comprising a zeolite powder and a mesh-like apparent density supporting the zeolite powder of 0.7 to 1.2, preferably 0.9 to 1.0. Floating zeolite composite.
(7) ゼォライト粉末とそれらを担持するテープ状の見掛け密度 0. 7〜1. 2 好ましくは 0. 9〜1. 0の担持体とより構成されてなることを特徴とするテー プ状の水中浮遊性ゼォライト複合物。  (7) Tape-like water characterized by comprising zeolite powder and a tape-like apparent density supporting them of 0.7 to 1.2, preferably 0.9 to 1.0 Floating zeolite composite.
(8) ゼォライト粉末とそれらを担持するハニカム状の見掛け密度 0. 7〜1. 2好ましくは 0. 9〜1. 0の担持体とより構成されてなることを特徴とするハ 二カム状の水中浮遊性ゼォライト複合物。  (8) Honeycomb-shaped, comprising a zeolite powder and a carrier having a honeycomb-shaped apparent density of 0.7 to 1.2, and preferably 0.9 to 1.0. Water-floating zeolite composite.
(9) ゼォライト粉末又は担持体が、 触媒作用を有するものであることを特徴と する前項 （1) 〜 （8) のいずれか 1項に記載の水中浮遊性ゼオライト複合物。  (9) The water-floating zeolite composite according to any one of the above (1) to (8), wherein the zeolite powder or the carrier has a catalytic action.
(10) ゼォライト粉末又は担持体が、 凝集助剤であることを特徴とする前項 （ 1) 〜 （8) のいずれか 1項に記載の水中浮遊性ゼオライト複合物。  (10) The water-floating zeolite composite according to any one of the above items (1) to (8), wherein the zeolite powder or the carrier is an aggregation aid.
(11) ゼォライト粉末又は担持体が、 吸着剤であることを特徴とする前項 （1 (11) The zeolite powder or the carrier is an adsorbent.
) 〜 （10) のいずれか 1項に記載の水中浮遊性ゼオライト複合物。 ) The water-floating zeolite composite according to any one of (1) to (10).
(12) ゼォライト粉末又は担持体が、 脱色剤であることを特徴とする前項 （1 ) 〜 （11) のいずれか 1項に記載の水中浮遊性ゼォライト複合物。  (12) The water-floating zeolite composite according to any one of the above (1) to (11), wherein the zeolite powder or the carrier is a decolorizing agent.
(13) ゼォライト粉末又は担持体が、 殺菌剤を担持してなるものであることを 特徴とする前項 （1) 〜 （12) のいずれか 1項に記載の水中浮遊性ゼォライト 複合物。  (13) The water-floating zeolite composite according to any one of the above (1) to (12), wherein the zeolite powder or the carrier carries a bactericide.
(14) ゼォライト粉末又は担持体が、 抗菌剤を担持してなるものであることを 特徴とする前項 （1) 〜 （12) のいずれか 1項に記載の水中浮遊性ゼォライト 複合物。  (14) The water-floating zeolite composite according to any one of the above (1) to (12), wherein the zeolite powder or the carrier carries an antibacterial agent.
(15) ゼォライト粉末又は担持体が、 有機物分解性微生物を担持してなるもの であることを特徴とする前項 （1) 〜 （14) のいずれか 1項に記載の水中浮遊 性ゼォライト複合物。 (15) Zeolite powder or carrier carrying organic matter-degrading microorganisms The water-floating zeolite composite according to any one of the above items (1) to (14), wherein:
(16) ゼォライト粉末又は担持体が、 酵素を担持してなるものであることを特 徴とする前項 （1) 〜 （15) のいずれか 1項に記載の水中浮遊性ゼオライト複 合物。  (16) The water-floating zeolite composite according to any one of the above (1) to (15), wherein the zeolite powder or the carrier carries an enzyme.
(17) 担持体が、 多孔質セラミックであることを特徴とする前項 （1) 〜 （1 6 ) のいずれか 1項に記載の水中浮遊性ゼォライト複合物。  (17) The water-floating zeolite composite according to any one of the above (1) to (16), wherein the support is a porous ceramic.
(18) 担持体が、 多孔質ガラスであることを特徴とする前項 （1) 〜 （16) のいずれか 1項に記載の水中浮遊性ゼォライト複合物。  (18) The water-floating zeolite composite according to any one of (1) to (16), wherein the support is a porous glass.
(19) 担持体が、 多孔質プラスチックであることを特徴とする前項 （1) 〜 （ 16) のいずれか 1項に記載の水中浮遊性ゼォライト複合物。  (19) The water-floating zeolite composite according to any one of (1) to (16), wherein the support is a porous plastic.
(20) ゼォライト又は担持体が凝集剤を担持してなるものであることを特徴と する前項 （1) 〜 （19) のいずれか 1項に記載の水中浮遊性ゼオライト複合物  (20) The water-floating zeolite composite according to any one of the above (1) to (19), wherein the zeolite or the carrier carries a flocculant.
(21) ゼォライトが、 ゼォライトクリスタロイド凝集剤であることを特徴とす る前項 （20) に記載の水中浮遊性ゼオライト複合物。 図面の簡単な説明 (21) The water-floating zeolite composite according to the above (20), wherein the zeolite is a zeolite crystalloid flocculant. BRIEF DESCRIPTION OF THE FIGURES
図 1〜5は、 各種形状の水中浮遊性ゼォライト複合物の断面図及び外観図を示 し、 図 1は中空体状の担持体 2表面にゼォライト粉末層 1が付着されてなるもの 、 図 2は繊維状の担体 3表面にゼォライト粉末層 1が付着されてなるもの、 図 3 はメッシュ状の担体 4表面にゼォライト粉末層 1が付着されてなるもの、 図 4は テープ状の担体 5表面にゼォライト粉末層 1が付着されてなるもの 、 図 5は、 ハニカム状の担体 6内面にゼォライト粉末層 1が焼結付着されてなるものを、 各 々示す。 符号の説明  1 to 5 show a cross-sectional view and an external view of a zeolite composite in water of various shapes, and FIG. 1 shows a zeolite powder layer 1 adhered to the surface of a hollow support 2. Fig. 3 shows a zeolite powder layer 1 attached to the surface of a fibrous carrier 3, Fig. 3 shows a zeolite powder layer 1 attached to the surface of a mesh-shaped carrier 4, and Fig. 4 shows a tape-shaped carrier 5 FIG. 5 shows a structure in which the zeolite powder layer 1 is adhered, and FIG. 5 shows a structure in which the zeolite powder layer 1 is sintered and adhered to the inner surface of the honeycomb-shaped carrier 6. Explanation of reference numerals
1 ：ゼォライト粉末層、  1: Zeolite powder layer,
2 ：中空体状の担持体、 3 ：繊維状の担持体、 2: a carrier in the form of a hollow body, 3: fibrous carrier,
4 ：メッシュ状の担持体、  4: mesh-shaped carrier,
5 ：テープ状の担持体、  5: tape-shaped carrier,
6 ：ハニカム状の担持体、 発明を実施するための最良の形態  6: Honeycomb-shaped carrier, best mode for carrying out the invention
以下に本発明の実施の形態について説明する。  Hereinafter, embodiments of the present invention will be described.
本発明のゼォライト複合物は、 水 （被処理水） 中において直ぐには沈降せずに 浮遊するものであって、 そのためゼォライトを見掛け密度 0 . 7〜1 . 2好まし くは 0 . 9〜1 . 0の担持体に担持させた構造としている。 被処理水の比重 （密 度） は、 水のみからなる場合は 1 . 0であるが、 泥状物等を含む懸濁液の場合は 、 1 . 1〜1 . 2であることもあり、 また、 アルコール等を含む場合は 1 . 0以 下となることもあるので、 これら各種の比重の液に対応した見掛け密度の担持体 が用いられる。  The zeolite composite of the present invention floats without immediately settling in water (water to be treated), and therefore has an apparent density of 0.7 to 1.2, preferably 0.9 to 1 The structure is such that it is carried on a carrier of. The specific gravity (density) of the water to be treated is 1.0 in the case of only water, but may be 1.1 to 1.2 in the case of a suspension containing a muddy substance. In addition, when alcohol or the like is contained, the concentration may be 1.0 or less, so a carrier having an apparent density corresponding to these various specific gravity liquids is used.
高純度のゼォライトは、 純度 9 9重量％以上の含水アルミノ珪酸塩であって、 珪礬比、 すなわち （S i〇2 と A 1 2 0 3 の重量組成の比） X I . 7、 が 3〜1 0の範囲のものであり、 すなわち、 ゼォライト A、 ゼォライト P (フィリップサ ィト） 、 ゼォライト X (フォージャサイト） 、 ゼォライト Y (フォージャサイト ) 及ぴヒドロキシソーダライトに相当するゼォライトである。 陽イオン交換容量 は4 0 0〜6 0 0。111 0 1 (+ ) k g—1であって、 いずれもそのゼォライトの構 造の理論値に相当するものである。 High purity Zeoraito is a pure 9 9 wt% or more hydrated aluminosilicate,珪礬ratio, i.e. (S I_〇 2 and A 1 2 0 3 composition by weight ratio) XI. 7, the 3 Zeolite A, zeolite P (phillipsite), zeolite X (fojasite), zeolite Y (fojasite) and zeolite corresponding to hydroxysodalite. The cation exchange capacity is 400-600.111 0 1 (+) kg- 1 and all correspond to the theoretical values of the structure of the zeolite.
また、 ゼォライトは、 珪酸及びアルミニウムを含む無機成分からなる非結晶性 の珪酸アルミニウム塩を含む組成物を、 アルカリ処理により人工的に転換して得 られ、 その主成分はフィリップサイト、 モルデナィト、 フォージャサイト、 ゼォ ライト入、 ヒドロキシソーダライトなどであり、 他の成分を少量含むこともある 。 また、 ゼォライ ト以外の部分、 すなわち非ゼォライト成分として、 有機物、 鉄 分、 その他の不純物及びゼォライトに至るまでの中間生成物なども共存するもの である。  Zeolite is obtained by artificially converting a composition containing an amorphous aluminum silicate salt composed of an inorganic component containing silicic acid and aluminum by alkali treatment, and its main component is philipsite, mordenite, and fauja. Site, zeolite, hydroxysodalite, etc., may contain small amounts of other components. In addition, organic substances, iron, other impurities, and intermediate products up to zeolite coexist as a part other than zeolite, that is, as a non-zeolite component.
そして、 珪酸及びアルミニウムを含む物質に、 0 . 1〜5 . O Nのアルカリ水 溶液を加え、 6 0〜2 8 0 °Cで加熱処理した後、 溶液部分を分離するが、 このと きの不溶残渣をアルカリ処理することによって、 ゼォライトを製造することがで きる。 Then, the substance containing silicic acid and aluminum is added with 0.1 to 5.ON alkaline water. After adding the solution and heat-treating it at 60 to 280 ° C, the solution part is separated. Zeolite can be produced by treating the insoluble residue at this time with alkali.
ゼォライト製造原料の珪酸及ぴアルミニウムを含む物質としては、 珪酸及びァ ルミニゥムが珪酸アルミニウム塩として含まれる物質であって、 火山灰、 軽石、 火山ガラスなどの降下火山噴出物、 石炭の焼却灰である石炭灰、 可燃性廃棄物の 焼却灰、 汚泥の焼却灰、 R D Fといわれるゴミ固形化燃料を熱源として燃焼させ た場合の焼却灰、 などを例示することができる。  The substances containing silicic acid and aluminum as raw materials for zeolite production include those containing silicic acid and aluminum as aluminum silicate salts. Examples include ash, incinerated ash of combustible waste, incinerated ash of sludge, and incinerated ash when burning solid waste fuel called RDF as a heat source.
前記の、 水中浮遊' I"生ゼォライト複合物は、 産業廃液、 都市排水等の汚染排水を 処理する際に、 撹拌により長時間にわたつて浮遊状態で排水と接触させること力 S でき、 その結果排水中の汚染物質をゼォライトに接触処理させて効率的に除去す ることができる。  The above-mentioned underwater floating 'I' raw zeolite composite can be used to treat polluted wastewater, such as industrial wastewater and municipal wastewater, for a long period of time by agitation to bring it into contact with the wastewater in a suspended state, and as a result, The pollutants in the wastewater can be efficiently removed by contacting the zeolite.
前記ゼォライトの担持体の形状は、 粒状体、 板状体のほか、 図 1〜5の各種形 状の水中浮遊性ゼオライト複合物の断面図及び外観図に示すごとき、 中空体、 繊 維体、 メッシュ状体、 テープ状体又はハニカム状体等であってよい。  The shape of the zeolite carrier may be a granular body, a plate-like body, a hollow body, a fiber body, It may be a mesh, a tape, a honeycomb, or the like.
なお、 図 1は中空体状の担持体 2表面にゼォライト粉末層 1が付着されてなる もの、 図 2は繊維状の担体 3表面にゼォライト粉末層 1が付着されてなるもの、 図 3はメッシュ状の担体 4表面にゼォライト粉末層 1が付着されてなるもの、 図 4はテープ状の担体 5表面にゼォライト粉末層 1が付着されてなるもの 、 図 5 は、 ハニカム状の担体 6内面にゼォライト粉末層 1が焼結付着されてなるものを 、 各々示しており、 図中、 1はゼオライト粉末層、 2は中空体状の担持体、 3は 繊維状の担持体、 4はメッシュ状の担持体、 5はテープ状の担持体、 6はハニカ ム状の担持体、 である。 また、 前記のゼォライト粉末又は担持体は、 触媒、 凝集助剤、 吸着剤、 脱色剤 、 殺菌剤、 抗菌剤、 有機物分解性微生物、 酵素等を担持してもよい。  Fig. 1 shows a zeolite powder layer 1 attached to the surface of a hollow carrier 2; Fig. 2 shows a zeolite powder layer 1 attached to the surface of a fibrous carrier 3; Fig. 3 shows a mesh Fig. 4 shows a tape-shaped carrier 5 with a zeolite powder layer 1 attached to the surface, and Fig. 5 shows a honeycomb-shaped carrier 6 with an inner surface of zeolite powder. The powder layer 1 is formed by sintering and adhering, respectively. In the figure, 1 is a zeolite powder layer, 2 is a hollow carrier, 3 is a fibrous carrier, and 4 is a mesh carrier. 5 is a tape-shaped carrier, and 6 is a honeycomb-shaped carrier. The zeolite powder or carrier may carry a catalyst, a coagulation aid, an adsorbent, a decolorizing agent, a bactericide, an antibacterial agent, an organic substance-degrading microorganism, an enzyme, and the like.
そして、 担持体が、 多孔質セラミック、 多孔質プラスチックであってよい。 さらに、 ゼォライト又は担持体は、 凝集剤を担持していてよく、 また、 ゼオラ イトクリスタロイド凝集剤であってもよい。 担持体の具体例としては、 例えば多数の単独孔を有する火山噴出物や黒曜石や 真珠岩を加熱膨張させたパーライト、 あるいは中空体状のガラス粒、 さらにはゥ レタンフォーム、 発泡スチロール等の発泡樹脂等があげられる。 Further, the carrier may be a porous ceramic or a porous plastic. Further, the zeolite or the carrier may support an aggregating agent, or may be a zeolite crystalloid aggregating agent. Specific examples of the carrier include volcanic ejecta having a large number of single holes, pearlite obtained by heating and expanding obsidian and perlite, or hollow glass particles, and foamed resin such as polyurethane foam and styrofoam. Is raised.
また、 担持体は、 活性炭、 銀ゼォライトのごとき抗菌剤、 有機汚染物質を栄養 源として分解する有機物分解性微生物、 あるいはアルコール飲料製造用等の酵素 類を担持してもよい。 本発明の好適な構成例として挙げられるものは、 担持体が有機物分解性微生物 を担持し、 その表面のゼォライトが凝集剤を担持してなる水中浮遊性ゼォライト 複合物であり、 同ゼオライト複合物を、 都市排水、 工場廃水等に投入して、 撹拌 すると、 まず懸濁物質が凝集剤、 例えば硫酸バンド、 ポリ塩ィヒアルミニウム、 又 はポリアクリルアミド系凝集剤によりフロック状に凝集して沈降されて清澄化し た透明水となり、 次いで同透明水中に溶解している有機汚染物質が担持体上の有 機物分解性微生物により消費分解される。 なお、 この微生物処理の際にはエアー レーシヨンを行う必要がある場合もある。  In addition, the carrier may carry an antibacterial agent such as activated carbon or silver zeolite, an organic substance-decomposing microorganism that decomposes organic pollutants as a nutrient source, or an enzyme for producing alcoholic beverages. A preferable configuration example of the present invention is a water-floating zeolite composite in which a carrier supports an organic substance-degrading microorganism, and a zeolite on the surface thereof supports a flocculant. When it is put into urban wastewater, industrial wastewater, etc., and stirred, the suspended substance is first flocculated and settled by flocculant, for example, a sulfate band, polychlorinated aluminum, or polyacrylamide-based flocculant. The water becomes clarified transparent water, and then the organic pollutants dissolved in the clear water are consumed and decomposed by the organically degrading microorganisms on the carrier. In addition, it may be necessary to perform air ration during the treatment of the microorganisms.
また、 前記清澄化された透明水中に細菌類が存在する場合には、 殺菌剤を担持 した、 担持体を使用することにより、 前記透明水を無害の飲用水となすことがで きる。  In addition, when bacteria are present in the clarified clear water, the use of a carrier carrying a bactericide makes the clear water harmless drinking water.
本発明の水中浮遊性ゼォライト複合を使用する処理対象水としては、 上記の他 に、 砂利廃水、 赤土含有廃水、 ヘドロ、 トンネル工事廃水、 活性汚泥水、 生活雑 廃水等が挙げられる。 産業上の利用可能性  The water to be treated using the water-floating zeolite composite of the present invention includes, in addition to the above, gravel wastewater, wastewater containing red soil, sludge, tunnel construction wastewater, activated sludge water, household wastewater, and the like. Industrial applicability
本発明のゼォライト複合物によれば、 水中において直ぐには沈降せずに浮遊さ せることができるため、 処理対象の各種廃水等と長時間接触させることができ、 その結果処理対象水をゼォライトで十分に効率的に処理することができる。  ADVANTAGE OF THE INVENTION According to the zeolite composite of this invention, since it can float in water without immediately settling out, it can be contacted with various wastewater to be treated for a long time, and as a result, zeolite can sufficiently treat the water to be treated. Can be efficiently processed.

Claims

請 求 の 範 囲 The scope of the claims
(1) ゼォライトとそれを担持する見掛け密度 0. 7〜1. 2担持体とより 構成されてなることを特徴とする水中浮遊性ゼォライト複合物。 (1) A water-floating zeolite composite comprising zeolite and an apparent density of 0.7 to 1.2 carrying the zeolite.
(2) ゼォライト粉末とそれらを表面に担持する見掛け密度 0. 7〜1. 2 の粒状の担持体とより構成されてなることを特徴とする粒状の水中浮遊性ゼオラ ィト複合物。  (2) A granular water-floating zeolite composite comprising zeolite powder and a granular support having an apparent density of 0.7 to 1.2 and supporting the zeolite on the surface.
(3) ゼォライト粉末とそれらを担持する見掛け密度 0. 7〜1. 2の板状 の担持体とより構成されてなることを特徴とする板状の水中浮遊性ゼオライト複 合物。  (3) A plate-like water-floating zeolite composite comprising zeolite powder and a plate-like carrier having an apparent density of 0.7 to 1.2 carrying them.
(4) ゼォライト粉末とそれらを担持する見掛け密度 0. 7〜1. 2の中空 体状の担持体とより構成されてなることを特@ [とする中空体状の水中浮遊性ゼォ ライト複合物。  (4) A hollow-body water-floating zeolite composite comprising a zeolite powder and a hollow-body-like support having an apparent density of 0.7 to 1.2 supporting the zeolite powder. object.
(5) ゼォライト粉末とそれらを担持する繊維状の見掛け密度 0. 7〜1. 2の担持体とより構成されてなることを特徴 する繊維状の水中浮遊性ゼォライ ト複合物。 (5) A fibrous underwater buoyant zeolite composite comprising zeolite powder and a fibrous carrier having an apparent density of 0.7 to 1.2 supporting the zeolite powder.
(6) ゼォライト粉末とそれらを担持するメッシュ状の見掛け密度◦. 7〜 1. 2の担持体とより構成されてなることを特徴とするメッシュ状の水中浮遊性 ゼォライト複合物。  (6) A mesh-like water-floating zeolite composite, comprising zeolite powder and a mesh-like apparent density supporting the zeolite powder;
(7) ゼォライト粉末とそれらを担持するテープ状の見掛け密度 0. 7〜1(7) Zeolite powder and tape-like apparent density carrying them 0.7 to 1
. 2の担持体とより構成されてなることを特徴とするテープ状の水中浮遊性ゼォ ライト複合物。 2. A tape-like water-floating zeolite composite, which comprises the support of (2).
(8) ゼォライト粉末とそれらを担持するハニカム状の見掛け密度◦. 7〜 1. 2の担持体とより構成されてなることを特徴とするハニカム状の水中浮遊性 ゼォライト複合物。  (8) A honeycomb-like water-floating zeolite composite comprising zeolite powder and a honeycomb-like apparent density supporting the zeolite powder and having a support of 7 to 1.2.
(9) ゼォライト粉末又は担持体が、 触媒作用を有するものであることを特 徴とする前項 （1) 〜 （8) のいずれか 1項に記載の水中浮遊性ゼオライト複合 物。 (9) The zeolite powder or the carrier has a catalytic action. The water-floating zeolite composite according to any one of (1) to (8), which is a feature.
(10) ゼォライト粉末又は担持体が、 凝集助剤であることを特徴とする前 項 （1) 〜 （8) のいずれか 1項に記載の水中浮遊性ゼオライト複合物。  (10) The water-floating zeolite composite according to any one of the above items (1) to (8), wherein the zeolite powder or the carrier is an aggregation aid.
(1 1) ゼォライト粉末又は担持体が、 吸着剤であることを特徴とする前項 (1) 〜 （10) のいずれか 1項に記載の水中浮遊 1·生ゼオライト複合物。 (11) The zeolite composite suspended in water according to any one of the above (1) to (10), wherein the zeolite powder or the carrier is an adsorbent.
(12) ゼォライト粉末又は担持体が、 脱色剤であることを特徴とする前項 (1) 〜 （11) のいずれか 1項に記載の水中浮遊性ゼオライト複合物。  (12) The water-floating zeolite composite according to any one of the above (1) to (11), wherein the zeolite powder or the carrier is a decolorizing agent.
(13) ゼォライト粉末又は担持体が、 殺菌剤を担持してなるものであるこ とを特徴とする前項 （1) 〜 （12) のいずれか 1項に記載の水中浮遊性ゼオラ ィト複合物。 (13) The water-floating zeolite composite according to any one of the above (1) to (12), wherein the zeolite powder or the carrier carries a bactericide.
(14) ゼォライト粉末又は担持体が、 抗菌剤を担持してなるものであるこ とを特徴とする前項 （1) 〜 （12) のいずれか 1項に記載の水中浮遊性ゼオラ ィト複合物。  (14) The water-floating zeolite composite according to any one of the above (1) to (12), wherein the zeolite powder or the carrier carries an antibacterial agent.
(15) ゼォライト粉末又は担持体が、 有機物分解性微生物を担持してなる ものであることを特徴とする前項 （1) 〜 （14) のいずれか 1項に記載の水中 浮遊性ゼォライト複合物。 (15) The water-floating zeolite composite according to any one of (1) to (14) above, wherein the zeolite powder or the carrier carries an organic matter-degrading microorganism.
(16) ゼォライト粉末又は担持体が、 酵素を担持してなるものであること を特徴とする前項 （1) 〜 （15) のいずれか 1項に記載の水中浮遊性ゼォライ ト複合物。  (16) The water-floating zeolite composite according to any one of the above (1) to (15), wherein the zeolite powder or the carrier carries an enzyme.
(17) 担持体が、 多孔質セラミックであることを特徴とする前項 （1) 〜 (16) のいずれか 1項に記載の水中浮遊性ゼォライト複合物。 (17) The water-floating zeolite composite according to any one of the above (1) to (16), wherein the support is a porous ceramic.
(18) 担持体が、 多孔質ガラスであることを特徴とする前項 （1) 〜 （1 6 ) のいずれか 1項に記載の水中浮遊性ゼォライト複合物。 (18) The water-floating zeolite composite according to any one of the above items (1) to (16), wherein the support is a porous glass.
(19) 担持体が、 多孔質プラスチックであることを特徵とする前項 （1) 〜 （16) のいずれか 1項に記載の水中浮遊性ゼオライト複合物。 (19) The water-floating zeolite composite according to any one of the above items (1) to (16), wherein the support is a porous plastic.
(20) ゼォライト又は担持体が凝集剤を担持してなるものであることを特 徴とする前項 （1) 〜 （19) のいずれか 1項に記載の水中浮遊性ゼオライト複 合物。  (20) The water-floating zeolite composite according to any one of (1) to (19) above, wherein the zeolite or the carrier carries a flocculant.
(21) ゼォライトが、 ゼォライトクリスタロイド凝集剤であることを特徴 とする前項 （20) に記載の水中浮遊性ゼオライト複合物。 (21) The water-floating zeolite composite according to the above (20), wherein the zeolite is a zeolite crystalloid flocculant.
PCT/JP2002/011986 2001-11-16 2002-11-18 Water-floating zeolite composites WO2003041837A1 (en)

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