WO2012137752A1 - Matériau adsorbant de substances organiques et support adsorbant de substances organiques comportant ledit matériau adsorbant de substances organiques - Google Patents

Matériau adsorbant de substances organiques et support adsorbant de substances organiques comportant ledit matériau adsorbant de substances organiques Download PDF

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WO2012137752A1
WO2012137752A1 PCT/JP2012/059029 JP2012059029W WO2012137752A1 WO 2012137752 A1 WO2012137752 A1 WO 2012137752A1 JP 2012059029 W JP2012059029 W JP 2012059029W WO 2012137752 A1 WO2012137752 A1 WO 2012137752A1
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organic substance
organic
water
soluble polymer
carrier
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PCT/JP2012/059029
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English (en)
Japanese (ja)
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安田　公昭
大井　隆志
吉田　隆
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国立大学法人名古屋大学
アキレス株式会社
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Priority to JP2012516428A priority Critical patent/JP5952187B2/ja
Publication of WO2012137752A1 publication Critical patent/WO2012137752A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/14—Diatomaceous earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/328—Polymers on the carrier being further modified
    • B01J20/3282—Crosslinked polymers
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/089—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials

Definitions

  • the present invention relates to an organic substance adsorbent. More specifically, the present invention relates to an organic substance adsorbing material having a novel structure and an organic substance adsorbing carrier containing the same.
  • Products that adsorb organic substances are widely used in various fields such as water treatment, agriculture, bioscience, and medical.
  • products that adsorb microorganisms are in the water treatment field
  • products that adsorb microorganisms, bacteria, viruses, pollen, dust, etc. are in the medical field
  • other products that adsorb organic substances are in the agricultural and bioscience fields. It is used.
  • a carrier whose surface is modified with a substance having a microorganism-adsorbing property is widely used as a wastewater treatment carrier having high microorganism adsorption performance, that is, high wastewater treatment efficiency.
  • a polyethylene imine porous body made of cellulose has been used.
  • This porous body has a structure in which polyethyleneimine is bonded to the surface of a porous body made of cellulose in order to increase the adsorption rate and density of microorganisms.
  • Polyethyleneimine is chemically bonded to the hydroxyl group of cellulose and covalently bonded to the porous body via a crosslinking agent.
  • Polyethyleneimine having primary, secondary, and tertiary amino groups is a water-soluble polymer having a highly branched resinous structure, and has the highest cationization density. Therefore, organic substances such as microorganisms whose cell membrane is negatively charged can be adsorbed at high density. As a result, the porous body made of cellulose combined with polyethyleneimine has various characteristics such as a high adsorption rate of microorganisms, a high adsorption density of microorganisms, and further, the adsorbed microorganisms are difficult to peel off.
  • the porous body made of cellulose undergoes biodegradation by enzymes produced by microorganisms, there is a problem that when it is used in a wastewater treatment tank for a long period of time, it gradually wears down and eventually disappears. Although it is possible to extend the lifetime by subjecting cellulose to a crosslinking treatment, it is difficult to completely suppress biodegradation. Therefore, when a polyethylene imine porous body made of cellulose currently on the market is used as a carrier for wastewater treatment, it is necessary to replenish the same carrier after a certain period of time, and management of wastewater treatment equipment And the cost of the carrier to be replenished must be taken into consideration. For this reason, a carrier having higher durability is demanded.
  • the cellulose porous body used as a carrier material has a complicated manufacturing process, so the manufacturing cost is high, and the carrier as a product in which polyethyleneimine is bonded to the cellulose porous body is inevitably expensive. It was.
  • a porous body made of synthetic resin that is also used as a carrier for wastewater treatment is cheaper than a porous body made of cellulose and has two advantages that it does not undergo biodegradation and does not wear out. There was a problem that the adsorption performance of microorganisms was inferior to that of the polyethyleneimine porous material made of cellulose.
  • Patent Document 1 a microorganism-immobilized carrier in which a thin film of polyethyleneimine resinized is formed on the surface of the carrier.
  • the microorganism-adsorbing carrier disclosed in Patent Document 1 has advantages that it is superior in durability and can be manufactured at a low cost compared to a conventional polyethylene imine porous body made of cellulose, and is made of a conventional synthetic resin. Compared to other porous bodies, it is excellent in microbial adsorption ability.
  • urethane having a hydroxyl group or the like when used as a carrier material, the polyethyleneimine film is difficult to peel off, but urethane itself is partially decomposed and weakened by oxides such as hypochlorous acid and ultraviolet rays. There was a weak point that the lifetime was about 5 years.
  • Patent Document 1 Even if the technique disclosed in Patent Document 1 is used for applications other than the microorganism-adsorbing carrier, the surface is covered with polyethyleneimine as in the case of the microorganism-adsorbing carrier, so that the durability is poor and practical use is not possible. It was n’t.
  • the main object of the present invention is to provide an organic adsorbent that is excellent in durability and organic adsorbability and that can be used in various fields, and an organic adsorbent carrier containing the organic adsorbent. To do.
  • the present inventors changed the idea from the conventional technique of coating the surface of an organic substance-adsorbing carrier such as a microorganism-adsorbing carrier with an organic substance-adsorbing material.
  • the present inventors have studied a specific organic adsorbent containing a water-soluble polymer, and have studied the inclusion of the organic adsorbent in a synthetic resin-based molded article constituting an organic adsorbent carrier, etc., leading to the completion of the present invention. .
  • the present invention first comprises a cationic water-soluble polymer for adsorbing organic matter, A crosslinking agent; It consists of diatomaceous earth in powder form, Provided is an organic substance adsorbent which is supported in a state where a crosslinked body of the water-soluble polymer is embedded in the diatomaceous earth.
  • a crosslinking agent consists of diatomaceous earth in powder form
  • an organic substance adsorbent which is supported in a state where a crosslinked body of the water-soluble polymer is embedded in the diatomaceous earth.
  • a powdery diatomaceous earth is adopted, and a specific water-soluble polymer crosslinked body that adsorbs organic matter is supported while embedded in the diatomaceous earth to produce an organic matter adsorbent having a novel structure. Succeeded in doing.
  • the type of the water-soluble polymer that can be used in the organic adsorbent according to the present invention is not particularly limited as long as the effects of the present invention are not impaired, but a water-soluble polymer having an amino group is preferably used. In this case, it is preferable to employ polyethyleneimine as the water-soluble polymer having an amino group.
  • the type of the crosslinking agent that can be used in the organic adsorbent according to the present invention is not particularly limited as long as the effects of the present invention are not impaired, but an epoxy derivative is preferably used. In this case, the epoxy derivative is preferably a polymer, and polyglycerol polyglycidyl ether is preferably employed.
  • the mixing ratio of the water-soluble polymer and the crosslinking agent is not particularly limited as long as the effect of the present invention is not impaired, and can be freely set. In the present invention, it is particularly preferable that the blending ratio of the water-soluble polymer and the crosslinking agent is 1 to 10: 1 by weight.
  • a novel organic material-adsorbing carrier in which the crosslinked water-soluble polymer is embedded in the synthetic resin as well as the surface of the synthetic resin is provided. Can do.
  • the “organic substance adsorbent” is an adsorbent to all substances constituting an organic body, that is, an animal or plant body. For example, those adsorbing microorganisms, bacteria, viruses, pollen, dust, etc. In the present invention, it is included in the “organic adsorbent”.
  • the present invention it is possible to provide an organic substance adsorbing material which is excellent in durability and organic substance adsorbability and can be used in various fields. Moreover, the organic substance adsorbent carrier comprising the organic substance adsorbent of the present invention in a synthetic resin can be used for a long period of time without the organic substance adsorbent falling off.
  • Organic substance adsorbent is an organic substance adsorbent composed of a water-soluble polymer, a cross-linking agent, and diatomaceous earth, and in a state where a cross-linked body of the water-soluble polymer is embedded in the diatomaceous earth. It is characterized by exhibiting a supported structure.
  • the organic substance adsorbent according to the present invention is only required to be supported in the diatomaceous earth in a state where the water-soluble polymer crosslinked body is at least embedded, for example, the water-soluble polymer crosslinked body is contained in the diatomaceous earth. Those embedded and supported on the surface of the diatomaceous earth are also included in the organic matter adsorbent of the present invention.
  • the organic adsorbent according to the present invention uses a cationic water-soluble polymer in order to adsorb organic substances.
  • the cationic water-soluble polymer that can be used in the organic adsorbent of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and can be used in an existing organic adsorbent. Any type of water-soluble polymer can be used as long as it has a functional group that reacts with the crosslinking agent.
  • a substance having a high cationization density is preferable, and a water-soluble polymer having an amino group is preferably used as an example of a substance having a high cationization density.
  • an alkyleneimine polymer for example, polyethyleneimine
  • polyacrylamide for example, polyacrylamide
  • polyamino acid for example, polylysine or polyarginine
  • the polyethyleneimine that is preferably used in the organic adsorbent of the present invention includes not only those having a linear structure but also those having a branched structure. Particularly in the present invention, polyethyleneimine having a branched structure containing primary, secondary and tertiary amines is preferred. Such polyethyleneimine can be synthesized, for example, by ring-opening polymerization of ethyleneimine in the presence of an acid catalyst.
  • the crosslinking agent is used for crosslinking the water-soluble polymer.
  • the crosslinking agent that can be used in the organic adsorbent of the present invention can be cross-linked by reacting with the functional group of the water-soluble polymer and does not impair the effects of the organic adsorbent of the present invention described later.
  • the type is not particularly limited, and any type of crosslinking agent that can be used for existing organic adsorbents can be used.
  • the water-soluble polymer having an amino group is used as the water-soluble polymer
  • the water-soluble polymer can be insolubilized by cross-linking each other through the amino group by using a crosslinking agent that is reactive with the amino group. it can.
  • the type of the crosslinking agent that is reactive with an amino group that can be used in the present invention is not particularly limited, and examples thereof include epoxy derivatives having one or more functional epoxy groups.
  • an epoxy derivative having two or more epoxy groups is particularly preferable.
  • Examples of the epoxy derivative that can be used in the present invention include ethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycidol, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Examples include sorbitol polyglycidyl ether and sorbitan diglycidyl ether. Among these, in the present invention, it is particularly preferable to employ polyglycerol polyglycidyl ether.
  • the mixing ratio of the water-soluble polymer and the crosslinking agent is not particularly limited, and can be appropriately set according to the use application of the organic substance adsorbent, the type of the water-soluble polymer and the crosslinking agent to be used, and the like.
  • the water-soluble polymer and the crosslinking agent are particularly preferably mixed at a weight ratio of 1 to 10: 1, more preferably 1 to 5: 1.
  • the amount of the water-soluble polymer that is not crosslinked can be minimized by setting the blending ratio of the water-soluble polymer to 10 or less by weight with respect to the crosslinking agent 1.
  • an organic adsorbent is used in water. At this time, it is possible to prevent the water-soluble polymer from being eluted in water and reducing the organic matter adsorptivity.
  • diatomaceous earth is used as a carrier for the water-soluble polymer and the crosslinking agent.
  • diatomaceous earth is not used, since it is difficult to pulverize only with the water-soluble polymer crosslinked body, it is difficult to apply to various uses.
  • diatomaceous earth as the carrier as in the present invention, for example, it is possible to pulverize the organic substance adsorbing material, and it can be applied to various uses.
  • Diatomaceous earth is an inorganic porous body mainly composed of silicon dioxide, and can retain a large amount of moisture and oil.
  • inorganic porous bodies include calcium carbonate, zeolite, sepiolite, aluminum oxide, silica, etc., but depending on the size of the pores, the water-soluble polymer crosslinked body may not be embedded, Moreover, the use may be limited. Therefore, in the present invention, diatomaceous earth was adopted because the supportability of the water-soluble polymer and the crosslinking agent and the use thereof can be applied to various fields.
  • Diatomaceous earth is also a chemically stable substance, excellent in heat resistance, and is a very bulky powder due to the porosity and unique shape of silicate shell. Therefore, the reaction material of the water-soluble polymer and the crosslinking agent for adsorbing the organic matter enters the pores of the diatomaceous earth, and the heat resistance of the organic matter adsorbing material of the present invention can be increased, leading to improved durability. .
  • the organic adsorbent according to the present invention has a very high heat resistance as compared with the conventional one. Therefore, when the organic adsorbent is applied to products in various fields, the water-soluble polymer is used in the production process. It is also possible to prevent the organic matter adsorptivity from being deactivated by heat.
  • a synthetic resin is used for the organic substance-adsorbing carrier described later, it is possible to select a synthetic resin having a relatively high melting point by using the organic substance-adsorbing material according to the present invention.
  • the diatomaceous earth used for the organic material adsorbent according to the present invention is in a granular state.
  • the diatomaceous earth that can be used in the present invention is not particularly limited as long as it is in a granular state, as long as the water-soluble polymer crosslinked body can be supported and the effects of the present invention are not impaired.
  • Diatomaceous earth with a particle size of less than 3 ⁇ m may not have sufficient pores to support the water-soluble polymer crosslinked body, and diatomaceous earth with a particle size of more than 50 ⁇ m is applied to products in various fields. From the viewpoint of maintaining a porous state sufficient to support the water-soluble polymer crosslinked product and being easily applicable to products in various fields, the particle size is 5 ⁇ m. More preferably, diatomaceous earth of 30 ⁇ m or less is employed.
  • the mixing ratio of the water-soluble polymer and the crosslinking agent is not particularly limited as long as the water-soluble polymer and the crosslinking agent can be supported so as to enter the pores of the diatomaceous earth. It is possible to set.
  • the water-soluble polymer and the reaction product of the crosslinking agent and the diatomaceous earth are preferably blended at a weight ratio of 1: 1 to 15. By using the above blending ratio, the reaction product of the water-soluble polymer and the crosslinking agent can be effectively taken into the pores of the diatomaceous earth, and there will be no hindrance to the mixing / kneading, drying and solidification, and pulverization processes described later. .
  • Such an organic adsorbent can be obtained by mixing and kneading water, a water-soluble polymer, a crosslinking agent, and diatomaceous earth, and drying and solidifying the mixture.
  • the particle size of the organic material adsorbent may be adjusted by pulverization after the solidification.
  • the organic adsorbent obtained as described above has a strong support of a water-soluble polymer having organic adsorbability, and can be used by being contained in various organic adsorbent carriers.
  • Organic substance-adsorbing carrier is one in which the organic substance adsorbing material described above is contained in a synthetic resin and formed into a shape suitable for the intended use.
  • the organic substance adsorbing carrier according to the present invention includes an organic substance adsorbing material in a synthetic resin, so that the organic substance adsorbing material is embedded not only on the surface of the resin but also inside. Therefore, the organic matter adsorptive carrier according to the present invention can solve the conventional problem that the water-soluble polymer is peeled and the adsorptivity is lowered, and the durability and the organic matter adsorptivity are very excellent.
  • the resin material and shape to be used are not particularly limited, it is possible to select a resin suitable for the intended use of the organic substance-adsorbing carrier, and it is possible to further enhance the durability of the organic substance-adsorbing carrier.
  • the synthetic resin that can be used in the organic matter-adsorbing carrier of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and specifically, polyacrylamide, polyvinyl alcohol, epoxy resin, polyester, polystyrene, Polyolefin resins represented by polyurethane, polypropylene and polyethylene are preferably used.
  • polyethylene is preferable because it is particularly resistant to oxidizing agents and ultraviolet rays and is not easily decomposed by microorganisms, and low-density polyethylene and linear low-density polyethylene are more preferable.
  • the organic adsorbent of the present invention is excellent in heat resistance, it is possible to select a resin having a relatively high melting point compared to conventional carriers, but low-density polyethylene and linear low-density polyethylene have a low melting point. Therefore, the molding temperature of the organic substance-adsorbing carrier can be kept low, and thermal denaturation of the water-soluble polymer contained in the organic substance-adsorbing material can be more reliably suppressed during the molding of the carrier.
  • the amount of the organic adsorbent added is not particularly limited, but the organic adsorbent is preferably contained in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the synthetic resin.
  • the organic substance adsorption performance can be expressed more reliably, and by setting it to 20 parts by weight or less, the deterioration of the mechanical properties of the organic substance adsorbent carrier is prevented, An increase in the weight of the organic substance-adsorbing carrier can also be prevented.
  • the organic matter adsorptive carrier of the present invention can be molded by adding an organic matter adsorbent to the total amount of the synthetic resin constituting the carrier, but when using a pellet-like resin such as an olefin resin, Dispersibility can be achieved by adding an organic adsorbent to a small amount of resin in advance to produce pellets containing the organic adsorbent, then dispersing the pellets in the remaining resin and forming the so-called master batch. From the point of view, it is preferable.
  • the organic substance-adsorbing carrier according to the present invention can be suitably used as a microorganism-adsorbing carrier when performing wastewater treatment using microorganisms.
  • the microorganism-adsorbing carrier purifies the wastewater by immobilizing microorganisms on the carrier and adsorbing and decomposing organic substances contained in the wastewater.
  • the microorganism-adsorbing carrier used for wastewater treatment or the like preferably contains an organic substance adsorbent in the above-mentioned synthetic resin, and the specific gravity is adjusted so that the specific gravity becomes 0.98 to 1.35 g / cm 3 .
  • the microorganism-adsorbing carrier By adjusting the specific gravity to 0.98 g / cm 3 or more, the microorganism-adsorbing carrier easily sinks in the wastewater treatment tank, and the wastewater treatment efficiency can be improved. Moreover, by adjusting the specific gravity to 1.35 g / cm 3 or less, it is possible to prevent weight from becoming difficult to handle, and the microorganism-adsorbing carrier sinks toward the lower layer of the wastewater treatment layer. It is possible to improve the wastewater treatment efficiency.
  • a specific gravity adjusting agent can be used to make the microorganism-adsorbing carrier have the above specific gravity.
  • the specific gravity adjuster is not particularly limited as long as the effect of the organic adsorbent of the present invention is not impaired, and any type of specific gravity adjuster can be used.
  • talc, calcium carbonate, magnesium carbonate, silica or the like can be used.
  • the shape of the microorganism-adsorbing carrier can be formed into any shape or size, such as cubic, rectangular, spherical, cylindrical, and can be hollow or solid, but a relatively small size is more resistant to wear. It is preferable that the diameter is about 3 to 20 mm square or about 3 to 20 mm.
  • the organic matter adsorptive carrier according to the present invention can be suitably used as an organic matter adsorption film. More specifically, the organic substance adsorbing material according to the present invention can be applied as a film for adsorbing organic substances by containing it in a synthetic resin and forming it into a film shape. This organic matter adsorption film can be applied to, for example, a fixed bed carrier for a wastewater treatment layer.
  • the organic matter adsorbing carrier according to the present invention can be suitably used as a nonwoven fabric for organic matter adsorption, knitted fabric, and woven fabric. More specifically, the organic substance adsorbing material according to the present invention is contained in a synthetic resin to form a fiber, and this fiber is bonded or entangled by heat, mechanical or chemical action, and applied as an organic substance adsorbing nonwoven fabric. Is possible.
  • This non-woven fabric for adsorbing organic substances can be used for cleaning tools such as masks, filters, gloves, mops, etc. in medical settings, etc., thereby adsorbing microorganisms, viruses, dust, etc., and contributing to prevention of nosocomial infections, for example. Is possible.
  • the organic substance adsorbing material can be used by being contained in various organic substance adsorbing carriers.
  • Example demonstrated below shows an example of the typical Example of this invention, and, thereby, the range of this invention is not interpreted narrowly.
  • Example 1 In Experimental Example 1, a microorganism-adsorbing carrier using the organic substance adsorbing material according to the present invention was produced, and the organic substance adsorbing property, chemical resistance, light resistance, abrasion resistance, and dispersibility in resin were examined.
  • zeolite product name “HSZ-700” manufactured by Tosoh Corporation
  • the mixture fluid is transferred to a container having a thickness of 50 mm, dried in an oven at 100 ° C. for 15 hours to obtain a water content of 1.5% or less, and an organic substance adsorbent mass is obtained and pulverized.
  • An organic adsorbent having an average particle size of 72 ⁇ m was obtained.
  • the viscosity was too high after the said drying, and it was not able to grind
  • a microorganism-adsorbing carrier was molded using the obtained organic substance adsorbent (only diatomaceous earth was used for Comparative Example 2).
  • the molding method is as follows. Add 100 parts by weight of low density polyethylene to 3 parts by weight of the organic adsorbents obtained in Examples 1-9 and Comparative Examples 1, 2, 4 to 6 and 20 parts by weight of talc, and extrude and cut to a length of 5 mm. Thus, a hollow microorganism-adsorbing carrier having an outer diameter of 5 mm and a wall thickness of 0.25 mm was obtained.
  • the obtained microorganism-adsorbing carrier was composed of 170 g of polyethyleneimine (product name “Epomin P-1000” (registered trademark) manufactured by Nippon Shokubai Co., Ltd.) and polyglycerol polyglycidyl ether (product name “Denacol EX-512” (registered trademark)).
  • Nagase ChemteX Co., Ltd. 45 g of water and 430 g of water were impregnated and dried to obtain a microorganism-adsorbing carrier having a surface coated with an organic adsorbent.
  • ⁇ Organic adsorption> Using synthetic waste water containing ammonium ions, a 20% microbial adsorbent carrier is introduced in an apparent volume into the waste water treatment layer container, and the nitrification rate is 0.5 kg-N / The evaluation was based on the number of days required to reach m3 ⁇ day or more. ⁇ ... Less than 15 days ⁇ ... 15 days or more but less than 20 days ⁇ ... 20 days or more but less than 25 days ⁇ ... 25 days or more NA ... Nitrification rate is 0.5kg-N / m 3. not more than day
  • the evaluation was as follows. ⁇ ⁇ ⁇ ⁇ Weight change is less than 2% ⁇ ⁇ ⁇ ⁇ Weight change is more than 2%
  • Light resistance was evaluated by a change in the surface state of the microorganism-adsorbing carrier after 100 hours of irradiation with a fade meter (under conditions of 80 ⁇ 3 ° C. and humidity of 50 ⁇ 5% or less). ⁇ ... Almost no change is observed. ⁇ ... Deteriorated and the surface becomes tattered.
  • ⁇ Abrasion resistance> In a 500 cc beaker with sandpaper of # 100 pasted on the entire inner surface, 400 cc of water and an apparent volume of 100 cc of a microbial adsorbent carrier are added and rotated at a speed of 400 rpm using a stirring blade, and microbial adsorption after 10 hours is performed.
  • the change in weight of the sex carrier was evaluated as follows. ⁇ ⁇ ⁇ ⁇ Weight change is less than 2% ⁇ ⁇ ⁇ ⁇ Weight change is more than 2%
  • Examples 1 to 9 using the organic adsorbent according to the present invention showed adsorptivity to microorganisms as organic substances.
  • Comparative Example 1 in which calcium carbonate was used instead of diatomaceous earth, organic matter adsorptivity could not be confirmed.
  • Comparative Example 4 using talc instead of diatomaceous earth
  • Comparative Example 5 using clay instead of diatomaceous earth
  • Comparative Example 6 using zeolite instead of diatomaceous earth, organic matter adsorptivity cannot be confirmed. It was.
  • Example 6 Examining each evaluation result based on the difference in the mixing ratio of the water-soluble polymer and the crosslinking agent, Example 6 in which the mixing ratio of the water-soluble polymer to the crosslinking agent 1 is less than 1 in weight ratio is slightly inferior in organic matter adsorption. I understood. On the contrary, it was found that in Example 7 in which the blending ratio of the water-soluble polymer with respect to the crosslinking agent 1 exceeds 10, the organic matter adsorptivity is good but the dispersibility is slightly inferior. From this result, it was found that a suitable blending ratio of the water-soluble polymer and the crosslinking agent is 1 to 10: 1 by weight.
  • Example 9 When each evaluation result by the difference in the blending ratio between the water-soluble polymer and the crosslinking agent and diatomaceous earth is examined, in Example 9 in which the blending ratio of the diatomaceous earth is less than 1 by weight with respect to the water-soluble polymer and the crosslinking agent 1, dispersion is performed. It was found that the properties were slightly inferior. On the contrary, in Example 8 where the blending ratio of diatomaceous earth with respect to the water-soluble polymer and the crosslinking agent 1 exceeds 15 by weight, it was found that the organic matter adsorptivity is slightly inferior. From these results, it was found that a suitable blending ratio of the water-soluble polymer and the crosslinking agent to diatomaceous earth was 1: 1 to 15 by weight ratio.
  • Example 2 In Experimental Example 2, when the organic substance adsorbing material according to the present invention was applied to a microorganism-adsorbing carrier used in water such as wastewater treatment, a suitable specific gravity was examined. Specifically, the specific gravity of the microorganism-adsorbing carrier was adjusted using talc as an example of a specific gravity adjusting agent, and the initial sedimentation property of each was examined.
  • Examples 10 to 14> Using the organic adsorbent according to Example 1 manufactured in Experimental Example 1, a microorganism-adsorbing carrier was obtained with the formulation shown in Table 2 below. Specifically, to 100 parts by weight of low density polyethylene, 3 parts by weight of the organic matter adsorbent according to Example 1 and talc in the proportions shown in Table 2 were added and extruded to be cut to a length of 5 mm. A hollow microorganism-adsorbing carrier having a diameter of 5 mm and a wall thickness of 0.25 mm was obtained.
  • the initial sedimentation and fluidity were evaluated based on the following evaluation criteria.
  • the microorganism-adsorbing carrier was put into the wastewater treatment layer, and the initial sedimentation property was evaluated from the ratio of the weight of the microorganism-adsorbing carrier floating on the water surface of the wastewater treatment layer after 1 hour.
  • the evaluation criteria are as follows.
  • the weight of the microorganism-adsorbing carrier floating on the water surface of the wastewater treatment layer is less than 1% of the input amount ⁇ ⁇ ⁇ ⁇ ⁇
  • the weight of the microorganism-adsorbing carrier floating on the water surface of the wastewater treatment layer is 1% or more of the input amount Less than 50% ⁇ ⁇ ⁇ ⁇
  • the weight of the microorganism-adsorbing carrier floating on the water surface of the wastewater treatment layer is 50% or more of the input amount.
  • the flowability of the microorganism-adsorbing carrier was evaluated according to the following criteria when a microorganism-adsorbing carrier having 400 cc of water and an apparent volume of 100 cc was put into a 500-cc beaker and rotated at a speed of 400 rpm using a stirring blade. .
  • a ... The microorganism-adsorbing carrier flows uniformly in the wastewater treatment layer.
  • the microorganism-adsorbing carrier flows slightly above or below the wastewater treatment layer, but has little effect on the wastewater treatment capacity.
  • the microorganism-adsorbing carrier is above or below the wastewater treatment layer. The wastewater treatment capacity is difficult to develop.
  • the organic substance-adsorbing carrier according to the present invention can adjust the specific gravity using a specific gravity adjusting agent such as talc.
  • the microorganism-adsorbing carrier having a larger specific gravity has less floating on the water surface of the wastewater treatment layer and is superior in initial sedimentation property.
  • the microorganism-adsorbing carrier having a large specific gravity is biased below the wastewater treatment layer, The adsorptive carrier is expected to flow in an upward direction above the wastewater treatment layer.

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Abstract

La présente invention concerne: un matériau adsorbant de substances organiques présentant une durabilité et une capacité d'adsorption de substances organiques supérieures, et les applications peuvent être utilisées dans une variété de domaines ; et un support adsorbant de substances organiques comportant ledit matériau adsorbant de substances organiques. La présente invention concerne un matériau adsorbant de substances organiques comportant de la terre de diatomées pulvérulente, un agent de réticulation, et un polymère cationique hydrosoluble pour l'adsorption de substances organiques, et cela se produit par le transport des corps réticulés du polymère hydrosoluble dans la terre de diatomées dans un état incorporé. Le support adsorbant de substances organiques comportant le matériau adsorbant de substances organiques dans une résine synthétique peut résoudre le problème classique de délaminage du polymère hydrosoluble et la diminution de la capacité d'adsorption, et présente une durabilité et une capacité d'adsorption de substances organiques nettement supérieures.
PCT/JP2012/059029 2011-04-07 2012-04-03 Matériau adsorbant de substances organiques et support adsorbant de substances organiques comportant ledit matériau adsorbant de substances organiques WO2012137752A1 (fr)

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JP2016211891A (ja) * 2015-04-30 2016-12-15 国立大学法人名古屋大学 懸濁態セシウムの除去方法
CN109264866A (zh) * 2018-09-11 2019-01-25 湖北理工学院 一种强化人工湿地脱氮的湿生植物纤维填料的制备方法及应用

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JPH07147981A (ja) * 1993-09-01 1995-06-13 Solvay Enzymes Inc 固定化酵素複合体の製造法および該方法により調製した固定化酵素複合体
JP2001128674A (ja) * 1999-11-09 2001-05-15 Bio Carrier Technology:Kk 不溶化された水溶性の微生物吸着性物質によりコーティングされた担体
JP2002013146A (ja) * 2000-06-28 2002-01-18 Shiima Consultant:Kk 法面安定化工法
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JP2009509513A (ja) * 2005-09-30 2009-03-12 ノボザイムス アクティーゼルスカブ 酵素の固定化

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016211891A (ja) * 2015-04-30 2016-12-15 国立大学法人名古屋大学 懸濁態セシウムの除去方法
CN109264866A (zh) * 2018-09-11 2019-01-25 湖北理工学院 一种强化人工湿地脱氮的湿生植物纤维填料的制备方法及应用

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