WO2009084936A2 - Agent adsorbant et son procédé de production - Google Patents

Agent adsorbant et son procédé de production Download PDF

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Publication number
WO2009084936A2
WO2009084936A2 PCT/KR2009/000008 KR2009000008W WO2009084936A2 WO 2009084936 A2 WO2009084936 A2 WO 2009084936A2 KR 2009000008 W KR2009000008 W KR 2009000008W WO 2009084936 A2 WO2009084936 A2 WO 2009084936A2
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Prior art keywords
adsorbent
weight
raw material
hours
carbon structure
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PCT/KR2009/000008
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English (en)
Korean (ko)
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WO2009084936A3 (fr
Inventor
Jae Shin Lim
Jung Hwan Park
Yong Soo Hwang
Bong Gon Kim
Jin Woo Kim
Do Gun Kim
Jong Cheol Yun
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Kavotech Co., Ltd.
Glonex Co., Ltd.
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Publication of WO2009084936A2 publication Critical patent/WO2009084936A2/fr
Publication of WO2009084936A3 publication Critical patent/WO2009084936A3/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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28095—Shape or type of pores, voids, channels, ducts
    • B01J20/28097—Shape or type of pores, voids, channels, ducts being coated, filled or plugged with specific compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the present invention relates to an adsorbent and a method for producing the same, and more specifically, to chemical and physical adsorption at the same time, and excellent adsorption properties for lipophilic and hydrophilic substances, such as fruits, vegetables and other horticultural crops
  • the present invention relates to a carbon / ceramic composite adsorbent having a multifunctional nanostructure capable of maintaining excellent freshness and a method of manufacturing the same.
  • Ethylene is a kind of plant hormone that promotes the maturation of fruits and the like before harvesting, but after harvesting, it promotes aging, tissue softening, decay and invasion of pathogens, causing degradation of quality, shortening of shelf life and selling time.
  • activated carbon As such, activated carbon, manganese peroxide (KMnO 4 ), and the like are used as materials used to remove ethylene causing decay of horticultural crops.
  • ethylene removal efficiency is decreased, and at the same time, there is a disadvantage in that the adsorbed material is re-released according to environmental changes such as temperature or humidity.
  • manganese peroxide is excellent in continuous ethylene removal effect, but because it is a toxic heavy metal can cause adverse effects on crops and the human body.
  • shredded fruits produce hydrogen sulfide, ammonia, amines and other irritating volatiles, which not only cause deterioration of quality and adverse effects on the human body, but also produce odors.
  • a deodorizing method for removing the odor a method using chlorine dioxide, a method of using a masking agent to conceal odorous substances, a method of picking a neutralizing agent in the air at a constant concentration, an adsorbent (ex. Activated carbon, charcoal and zeolite) And the like) are used.
  • the method using the masking agent is difficult to remove the fundamental odor due to its strong fragrance, and can react with the malodorous substance to generate a third substance, which causes a lot of safety problems.
  • the pickling method using the neutralizing agent itself has a smell, it is difficult to control the exact concentration, there is a problem that is harmful to the human body by the generation of by-product gas as well as damage to the crop when excessive use.
  • the adsorbent deteriorates the adsorption effect in the presence of excessive moisture, and in some cases, the horticultural crops may be dried to reduce the freshness, and the adsorbed organic substances may cause harmful growth of bacteria to the horticultural crops. There are disadvantages.
  • Japanese Laid-Open Patent No. 1979-53669 discloses a method of producing a product by molding by adding bentonite or the like to a mixture of zeolite and activated carbon, followed by drying and firing.
  • bentonite since bentonite is used as a binder, the bentonite occludes pores of activated carbon at a high temperature, so that the specific surface area and the adsorption effect are remarkably inferior.
  • Japanese Laid-Open Patent No. 1984-69146 discloses a method of preparing an adsorbent by adding a silicate compound to activated carbon.
  • the silicate compound also has the risk of blocking the pores of activated carbon, and has the disadvantage of inferior hydrophilicity and adsorptivity.
  • Korean Patent No. 1994-18327 discloses a technique for preparing a product by mixing an inorganic and organic binder with a mixture of zeolite and activated carbon.
  • a technique for preparing a product by mixing an inorganic and organic binder with a mixture of zeolite and activated carbon there is a high possibility that activated carbon pores are blocked by performing a sintering process during manufacturing.
  • the present invention can simultaneously perform chemical and physical adsorption, and excellent adsorption properties for lipophilic and hydrophilic substances, effectively remove ethylene, a mature decaying hormone, such as fruits, vegetables and other horticultural crops, and antibacterial and bactericidal effect It aims at providing the adsorbent which can maintain the freshness, such as fruit, and its manufacturing method outstandingly.
  • the present invention as a means for solving the above problems, a matrix containing a porous carbon structure present in a layered state; And it provides an adsorbent comprising a ceramic material present in the pores of the carbon structure.
  • the present invention as another means for solving the above problems, the first step of mixing the raw material and the modifier; A second step of mixing the mixture of the first step and the solution of gelatinizer; A third step of insolubilization of the mixture of the second step; Carbonizing and activating the insoluble mixture to produce a porous carbon structure; And a fifth step of growing the ceramic in the pores of the porous carbon structure.
  • the adsorbent of the present invention can simultaneously perform chemical and physical adsorption, and has excellent adsorption properties for lipophilic and hydrophilic substances, effectively removing ethylene, a mature decaying hormone, such as fruits, vegetables and other horticultural crops, It exhibits a bactericidal effect and can maintain excellent freshness of fruits and the like.
  • Example 1 is a SEM analysis result of analyzing the particle diameter of the ceramic material (zeolite Y-type) contained in the adsorbents prepared in Examples 2 to 4 of the present invention.
  • Figure 2 is a cold storage warehouse test results of the fruit of the nano-adsorbent according to an embodiment of the present invention.
  • the present invention is a matrix containing a porous carbon structure present in a layered state.
  • It relates to an adsorbent comprising a ceramic material present in the pores of the carbon structure.
  • the adsorbent of the present invention can simultaneously perform chemical and physical adsorption, and has excellent adsorption properties for lipophilic and hydrophilic substances, effectively removing ethylene, a mature decaying hormone, such as fruits, vegetables and other horticultural crops, It exhibits a bactericidal effect and can maintain excellent freshness of fruits and the like.
  • the adsorbent of the present invention preferably has an average particle diameter of 20 mesh to 100 mesh, more preferably 30 mesh to 70 mesh.
  • the specific surface area of the adsorbent of the present invention is preferably 700 m 2 / g to 1500 m 2 / g, and the apparent bulk density is preferably 0.25 to 0.5. If the average particle diameter, specific surface area and / or apparent specific gravity are controlled within the above range, the adsorbent of the present invention can exhibit more excellent adsorption efficiency.
  • the adsorbent of the present invention includes a porous carbon structure present in a layered state, wherein each layered carbon structure preferably has a cyclic structure.
  • the carbon structure may be activated carbon formed from vegetable raw materials and / or fossil raw materials.
  • Examples of the vegetable raw material may include palm shell, bamboo, oak, rice hull, apricot seed, peach seed or jujube seed, and examples of fossil raw material may include coal ash, coal, coal-based pitch or petroleum-based pitch.
  • the present invention is not limited thereto.
  • the porous carbon structure (activated carbon) of the present invention may be prepared from a mixture of one or more kinds of vegetable raw materials and fossil raw materials as described above, preferably from mixed raw materials of vegetable and fossil raw materials, and more preferably. May be prepared from mixed raw materials of rice hull, bamboo and coal-based pitch.
  • the rice hull is a by-product of rice planting, and contains crude fiber, soluble sugars, pollen, and crude protein, and about 90% of the pollen is composed of organic silica having excellent reactivity.
  • the chaff also contains radially developed macropores on the order of micrometers, and also contains organic silica, cellulose, nigreen, low boiling organic materials and the like.
  • the organic silica is converted into a nano-scale ceramic material in the process of manufacturing activated carbon, which may act as a nucleus for growth of the adsorbent micelles included in the adsorbent.
  • the term “adsorbed micelle or admicelle” refers to a component capable of adsorbing and removing toxic substances or odor causing substances that may adversely affect the freshness of fruits, vegetables, and other horticultural crops. Specifically, it may mean a ceramic material included in the porous carbon structure or metal nanoparticles described below. In addition, low-boiling organic materials and the like contained in chaff and the like may be converted into a base wall or a binder of the activated carbon (carbon structure) to be produced.
  • the bamboo is a subtropical woody plant, which is composed of a soft portion and a hard portion, the soft portion as a water pipe for supplying water and nutrients during growth includes a large pore of about 100 ⁇ m in a straight form. Therefore, the soft portion may also act as a nucleus for growth of adsorption micelles in the manufacturing process, and the low molecular weight organic material and nigrin included in bamboo may play a role of reinforcing the base wall of the carbon structure (activated carbon). .
  • the fossil raw material may form a high molecular weight organic material and tar in the process of manufacturing activated carbon, thereby acting to strengthen the bonding strength of the prepared activated carbon and the strength of the base wall. Accordingly, the fossil raw material serves to reinforce the low strength of the carbon structure (activated carbon) produced from the vegetable raw material.
  • the carbon structure of the present invention may be formed from the vegetable raw materials and / or fossil raw materials as described above, and more preferably from the mixed raw material containing 10 parts by weight to 40 parts by weight of fossil raw materials with respect to 100 parts by weight of the vegetable raw materials. Can be.
  • the carbon structure has a porous structure including a plurality of pores, wherein the pores included in the porous structure may have a cyclic structure.
  • the average diameter of the pores included in the porous structure may be preferably 50 nm to 100 nm. When the said average diameter is less than 50 nm or exceeds 100 nm, there exists a possibility that the adsorption efficiency of an adsorbent may fall.
  • the adsorbent of the present invention includes a ceramic material contained in the pores of the porous carbon structure contained in the matrix described above.
  • the ceramic material is preferably a crystalline material having an average particle diameter of 1 nm to 30 nm. If the particle diameter is less than 1 nm, the adsorption efficiency of the adsorbent may be lowered, and if it is more than 30 nm, the doping efficiency to the carbon structure may be lowered.
  • Ceramic materials that can be used in the present invention are selected from the group consisting of silica (SiO 2 ), amorphous aluminosilicate, zeolite (ex. Zeolite X, zeolite Y, zeolite ⁇ ), ZSM (Zeolite Molecular Sieve) -5, and the like.
  • silica SiO 2
  • zeolite ex. Zeolite X, zeolite Y, zeolite ⁇
  • ZSM Zerolite Molecular Sieve
  • the ceramic material may be formed by a gelling reaction of a colloidal solution containing sodium aluminate or sodium hydroxide and organic silica in the process of preparing the adsorbent of the present invention. More specifically, in the preparation of the adsorbent of the present invention, the organic silica contained in the raw material is first converted into amorphous aluminosilicate, and then formed into a crystalline ceramic material.
  • the ceramic material as described above is preferably included in the amount of 0.1 parts by weight to 60 parts by weight with respect to 100 parts by weight of the carbon structure in the adsorbent of the present invention. If the content is less than 0.1 part by weight, the adsorption efficiency of the adsorbent may be lowered. If it is more than 60 parts by weight, the pores of the carbon structure may be blocked.
  • the adsorbent of the present invention may also further comprise metal nanoparticles introduced on the surface of the ceramic material.
  • metal nanoparticles that can be used at this time include, but are not limited to, one or more of Ag, Pd, Pt, Au, TiO 2 , Fe, Zn, or Cu.
  • the metal nanoparticles are transition metal nanoparticles; And noble metal material formed on the surface of the transition metal nanoparticle. That is, in the present invention, the metal nanoparticles preferably have a form in which a noble metal component is coated on the surface of the nano-level transition metal.
  • the transition metal may include at least one selected from the group consisting of Fe, Zn, Cu, and Ti (or TiO 2 ), and examples of the precious metal may include one selected from the group consisting of Ag, Pd, Pt, and Au.
  • the average particle diameter of the metal nanoparticles is preferably 1 nm to 20 nm. If the particle size is less than 1 nm, the adsorption performance due to the metal nanoparticles may not be exhibited. If the particle size exceeds 20 nm, the doping efficiency to the adsorbent may be lowered.
  • the particle diameter of the transition metal is about 1 nm to 30 nm (preferably about 20 nm), and the thickness of the noble metal layer adsorbed on the surface thereof. May be about 0.1 nm to 0.5 nm (preferably about 0.2 nm).
  • the adsorbent of the present invention may include such metal nanoparticles in a concentration of about 100 ppm to 10,000 ppm, but is not limited thereto.
  • the invention also includes a first step of mixing a raw material and a modifier; A second step of mixing the mixture of the first step and the solution of gelatinizer; A third step of insolubilization of the mixture of the second step; Carbonizing and activating the insoluble mixture to produce a porous carbon structure; And a fifth step of growing the ceramic in the pores of the porous carbon structure.
  • the raw material and the modifier are mixed.
  • the raw material that can be used in the first step may be various vegetable raw materials and / or fossil raw materials as described above, and among them, it is preferable to use a mixed raw material of vegetable and fossil raw materials, and in particular, chaff, bamboo and coal-based pitches are used. It is preferable to use.
  • the fossil raw material is preferably 10 parts by weight to 40 parts by weight based on 100 parts by weight of the vegetable raw material.
  • the mixed raw material when using a mixed raw material of rice husk, bamboo and coal pitch as the raw material, the mixed raw material includes 10 parts by weight to 50 parts by weight, 20 parts by weight to 90 parts by weight of bamboo and 10 parts by weight to 40 parts by weight of coal-based pitch can do.
  • each raw material in the first step of the present invention may be carried out a process of grinding each material to be used to a predetermined size and then mixing, wherein each raw material is 100 mesh or less, preferably 80 mesh or less May be ground and classified.
  • the modifier mixed in the first step serves to convert the linear low molecular weight material generated in the insolubilization and carbonization process of the raw material into the high molecular weight material of the side chain.
  • low molecular weight material or "high molecular weight material” used in the present invention is a concept that collectively refers to the organic material generated from the raw material in the manufacturing process of the adsorbent, which can be finally converted to a porous carbon structure.
  • Examples of modifiers that can be used in the present invention include one or more selected from the group consisting of styrene butadiene styrene (SBS), nitro benzene and nitrile butadiene rubber (NBR), of which nitro benzene This is preferable.
  • the modifier is preferably mixed in an amount of 0.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the raw material, and more preferably 5 parts by weight to 15 parts by weight. If the content is less than 0.5 parts by weight, there is a fear that the reforming does not proceed, if more than 20 parts by weight, excessive reforming reaction proceeds, there is a fear that the physical properties of the adsorbent rather deteriorates.
  • the mixture prepared in the first step is mixed with the colloidal solution, and thus, in the second step, the gelatinization reaction may proceed.
  • the colloidal solution used above may be, for example, an aqueous solution containing sodium aluminate (NaAlO 2 ) and / or sodium hydroxide (NaOH), wherein the sodium aluminate and sodium hydroxide are both in the same aqueous solution. It may be included or prepared as a separate aqueous solution and mixed with the mixture of the first step.
  • sodium aluminate may be prepared by, for example, reacting aluminum hydroxide with sodium hydroxide in an aqueous solution containing a surfactant, wherein the reaction formula for preparing sodium aluminate is as follows.
  • the kind of surfactant that may be included in the aqueous solution in which the reaction proceeds may be one kind or two or more kinds of gelatin, alginate, carboxyl methylcellulose (CMC), cationic surfactant or anionic surfactant, which is 5 weight in the aqueous solution. It may be included in an amount of 20% by weight.
  • CMC carboxyl methylcellulose
  • reaction for producing sodium aluminate as described above may be performed for 1 hour to 2 hours at a temperature of 100 ° C. to 130 ° C., for example.
  • the gelatinization reaction of sodium aluminate and / or sodium hydroxide contained in the colloidal solution and (organic) silica contained in the raw material may proceed.
  • organic silica included in the raw material is grown into a silica network structure by a sol-gel process, and finally, a ceramic material such as zeolite is grown.
  • Such a gelatinization reaction may proceed via a reaction as shown in the following scheme.
  • the mechanism of the schemes presented below is only one example where the gelation reaction of the present invention is carried out.
  • R in the above scheme means a group formed by alkyl, alkenyl, alkynyl or other organic material.
  • the organic silica present in the raw material may be grown into a network structure of amorphous aluminosilicate using sodium hydroxide or the like present in the colloidal solution as a catalyst (Scheme 5 and 6).
  • the gelation reaction of the present invention in the above process, by adjusting the molecular size of the network structure by the action of sodium aluminate contained in the colloidal solution, it is possible to produce a nano-sized ceramic material. That is, the sodium aluminate can inhibit the diffusion of the reactants and control the reaction.
  • the organic silica contained in the raw material (ex. Chaff) is used as the stationary phase reactant, and reacted with the fluidized phase reactant (ex. Sodium aluminate and / or sodium hydroxide, etc.) to achieve a constant size and arrangement of nano size. Eggplant can obtain the desired material.
  • the content of each component of the raw material and the colloidal solution is controlled so that the molar ratio between the specific reactants generated in the course of the colloidal reaction can be optimized. It is desirable to.
  • the molar ratio (SiO 2 / Al 2 O 3 ) of the silica and aluminum oxide generated in the gelling reaction is 1 to 100, preferably Preferably from 2.5 to 60, more preferably from 3 to 60. If the molar ratio is less than 1, the formation of ceramic (ex. Zeolite) crystals may be inhibited. If the molar ratio exceeds 100, ceramic crystals of desired physical properties may not be produced.
  • the molar ratio (Na 2 O / SiO 2 ) of sodium oxide and silica generated in the gelatinization reaction is 0.1 to 3.0, preferably May be controlled to be 0.095 to 1.52. If the molar ratio is less than 0.1, the formation of ceramic (ex. Zeolite) crystals may be inhibited. If the molar ratio exceeds 3.0, ceramic crystals of desired physical properties may not be produced.
  • the content of the raw material and the like may be controlled such that the molar ratio (H 2 O / Na 2 O) of water and sodium oxide, which are solvents of the gelation process, is 10 to 100. If the molar ratio is less than 10, ceramic crystals of desired physical properties may not be produced. If the molar ratio exceeds 100, ceramic crystals may not be produced.
  • the content of the raw material of sodium aluminate contained in the colloidal solution is 0.8% to 6% by weight
  • the raw material of sodium hydroxide The content of the contrast may be 1.5% to 14% by weight
  • the content of the solvent used, ie water may be 80% to 98% by weight, preferably 30% to 40% by weight relative to the raw material.
  • each of the above contents is only one aspect of the present invention, which is not particularly limited so long as it is controlled so that the molar ratio in the above-described range can be achieved.
  • the gelatinization reaction in the second step of the present invention is 20 minutes to 6 hours, preferably 20 minutes to 2 hours, more preferably at a temperature of 20 °C to 80 °C, preferably 30 °C to 60 °C May be performed for 30 minutes to 1 hour.
  • the said temperature is less than 20 degreeC, there exists a possibility that reaction rate may fall, and when it exceeds 80 degreeC, reaction rate may become too fast and an unintentional by-product may be produced.
  • the reaction time is less than 20 minutes, the ceramic (ex. Zeolite) may not grow sufficiently, and if it exceeds 6 hours, the ceramic crystal of the desired type may not be produced.
  • the material subjected to the gelatinization in the same manner may include a mixed powder (vegetable raw material and / or fossil raw material), amorphous aluminosilicate, sodium hydroxide and / or water)
  • the material subjected to the gelatinization may be formed into a spherical, particulate or straight (bar type) form, which is carried out using a conventional centrifugal spherical molding machine, injection molding machine, extrusion molding machine or liquid molding machine, etc. can do.
  • drying process may be carried out at a temperature of about 20 °C to 80 °C, preferably 40 °C to 60 °C.
  • the insolubilization reaction of the mixture which has undergone the above-mentioned colloidal reaction is carried out, and in this step, the low boiling point material generated by pyrolysis of the raw material is converted into a high boiling point material, and more specifically, The low molecular weight linear organic material is converted into a high molecular weight cyclic compound.
  • the low boiling point organic material generated by pyrolysis of the raw material is reacted with the above-described modifier to be converted into a high boiling point material having a ring structure having a branched chain.
  • the cyclic compound is finally converted to a carbon structure.
  • This third step of the present invention is followed by the second step described above, after the reaction temperature is raised to 150 °C to 350 °C, preferably 250 °C to 450 °C at a rate of 5 °C / min to 10 °C / minute
  • the reaction temperature is 150 ° C. If less, the polymerization reaction may not be initiated. If it exceeds 350 ° C, the side chain ring structure may be damaged.
  • the temperature increase rate is less than 5 degree-C / min in the 3rd step of this invention, there exists a possibility that reaction may take a long time, and when it exceeds 10 degree-C / min, there exists a possibility that the target high boiling point cyclic compound may not be produced
  • the third step of the present invention may also use a gas containing oxygen (O 2 ) as a catalyst, wherein the concentration of oxygen may be 5 vol% to 20 vol% of the raw material. If the concentration is less than 5 vol%, the reforming reaction may not proceed, and if it exceeds 20 vol%, there may be a combustion phenomenon in the reaction system.
  • the other components of the oxygen-containing gas are not particularly limited, and for example, nitrogen (N 2 ) can be used.
  • the raw material may include amorphous aluminosilicate, a cyclic carbon compound, and / or sodium hydroxide.
  • the fourth step of the present invention is to prepare a carbon structure by carbonizing and activating the high boiling cyclic compound generated by the insolubilization treatment.
  • the cyclic compound generated in the third step is converted to a carbon structure having a layered carbon ring structure through deoxygenation and dehydrogenation.
  • This carbonization process is carried out at a temperature of 500 ° C to 800 ° C, preferably 600 ° C to 700 ° C under a reducing atmosphere.
  • a temperature of 500 ° C to 800 ° C, preferably 600 ° C to 700 ° C under a reducing atmosphere.
  • the said temperature is less than 500 degreeC, there exists a possibility that a layered carbon structure may not produce
  • the carbonization reaction time is preferably 0.5 hours to 6 hours, more preferably 2 hours to 4 hours.
  • the said time is less than 0.5 hour, there exists a possibility that a carbon structure agent may not be produced
  • the type of the reducing gas is not particularly limited, for example, nitrogen. (N 2) gas may be mentioned.
  • an activation process of forming pores in the carbon structure is performed.
  • the method of this activation process is not particularly limited and can be carried out, for example, by treating the carbide with an activator of 1 to 5 times, preferably 1.5 to 2 times the volume of carbide.
  • the activator include, but are not limited to, water vapor, carbon dioxide, air or potassium hydroxide.
  • the activation process is preferably carried out at a temperature of 700 °C to 950 °C, preferably 850 °C to 900 °C, 0.5 hours to 12 hours, preferably 2 hours to 6 hours. If the temperature is less than 700 ° C or the activation time is less than 0.5 hours, there is a fear that the activation does not occur efficiently, if the temperature exceeds 900 ° C, or if the activation time exceeds 12 hours, the yield of the final product may be lowered. .
  • the carbonization and activation process may be a material including a layered ring carbon structure, amorphous aluminosilicate, and / or sodium hydroxide, which enters the fifth step.
  • the fifth step of the present invention is to hydrothermally process a raw material that has undergone the carbonization and activation process of the fourth step to grow a ceramic material in the pores of the structure.
  • the amorphous aluminosilicate contained in the raw material in the step may be grown with a ceramic material such as crystalline zeolite or silica.
  • the nuclear growth and crystallization of the ceramic material proceeds, and the nuclear growth process is performed by comparing an aqueous alkali solution (eg, sodium hydroxide aqueous solution) having a concentration of 1% by weight to 12% by weight with respect to the volume of the mixture that has undergone the fourth step. It can be added in a volume of 0.5 to 4 times and reacted at a temperature of 25 ° C. to 250 ° C. for 1 to 24 hours. At this time, when the concentration of the aqueous alkali solution is less than 1% by weight or more than 12% by weight, there is a concern that a ceramic material of a desired crystalline form may not be produced.
  • an aqueous alkali solution eg, sodium hydroxide aqueous solution
  • reaction temperature is less than 25 degreeC, there exists a possibility that reaction rate may fall, and when it exceeds 250 degreeC, there exists a possibility that the target crystalline ceramic material may not be formed.
  • reaction time is less than 1 hour or exceeds 24 hours, there exists a possibility that the target crystalline ceramic material may not be produced.
  • a crystallization process may be performed after the nuclear growth process as described above.
  • the process may be performed at a temperature of 80 ° C. to 250 ° C. for 2 hours to 24 hours.
  • the said temperature is less than 80 degreeC, there exists a possibility that reaction rate may fall, and when it exceeds 250 degreeC, there exists a possibility that the ceramic material of an unintentional type may be formed.
  • the reaction time is less than 2 hours or more than 24 hours, there is a fear that an unintended type of ceramic material is formed.
  • the step of introducing the metal nanoparticles to the ceramic material formed in the pores of the carbon structure may be further performed.
  • the method of introducing the metal nanoparticles is not particularly limited, for example,
  • Synthesizing the metal nanoparticles in the solvent in the above for example, (a) injecting a precursor of the metal nanoparticles in an aqueous solution containing a surfactant; And (b) reacting the aqueous solution into which the precursor is added at a temperature of 25 ° C. to 90 ° C. for 2 hours to 6 hours.
  • surfactant examples include gelatin, alginate, CMC (Carboxyl methylcellulose) or EVA (Ethylene vinylacetate) or two or more kinds thereof, which is 2% by weight in an aqueous solution. To 20% by weight, preferably 5% to 10% by weight.
  • step (a) of the present invention when the precursor of the metal nanoparticles is added to the aqueous solution containing the surfactant as described above, the precursor may be added in a state dissolved in a suitable solvent (ex. Distilled water).
  • a suitable solvent ex. Distilled water
  • the precursor may be added in the form of a complex by reacting the precursor with an appropriate chelating agent (ex. Ammonia).
  • Examples of the precursor of the metal nanoparticles that can be used at this time include metal halides, metal nitrides or metal oxides, and specifically, AgNO 3 , PdCl 2 , TiCl 4 , FeCl 2 , Fe (NO 2 ) 2 , ZnCl 4 and Cu [(NO) 3 ] 2, and the like, or a metal salt of two or more kinds, and the like, but are not limited thereto.
  • the precursor of the metal nanoparticles as described above may be added to the surfactant-containing aqueous solution over about 2 hours to 4 hours in the temperature range of about 20 °C to 40 °C.
  • step (b) of the present invention a step of reducing the precursor of the metal nanoparticles introduced in the same manner as described above, which step is carried out at a temperature of about 25 °C to 90 °C, preferably about 60 °C to 90 °C, about 2 It may be carried out by reacting for hours to 6 hours, preferably about 3 to 4 hours.
  • the step (b) may be performed in a state in which the pH of the solution is adjusted to about 10 to 13 using an appropriate pH adjuster (ex. NaOH, KOH and / or Na 2 CO 3 ).
  • the pH of the solution can be adjusted to a range of 9 to 12, the reaction after dropping is at a temperature of 25 °C to 40 °C, about 2 hours to 6 hours More preferably 3 to 4 hours.
  • the metal nanoparticles may also be further performed to reduce the remaining precursor for 2 to 4 hours at a temperature of about 80 °C.
  • step (2) of the present invention a carbon structure is immersed in a solution containing the metal nanoparticles (or nanoparticles having a noble metal adsorbed on a transition metal) prepared in step (1), thereby converting the metal nanoparticles into a carbon structure.
  • the step of introducing into the ceramic material. At this time, the introduction of the metal nanoparticles may be carried out at a temperature of 25 °C to 100 °C, preferably 25 °C to 80 °C.
  • the concentration of the metal nanoparticles in the solution in the solution in which the carbon structure is immersed may be 100 ppm to 10,000 ppm, preferably 500 ppm to 3,000 ppm, the volume of the solution is 1 to 4 times the volume of the carbon structure It may be a boat.
  • the metal nanoparticles are also introduced into the ceramic material of the carbon structure as described above, and then dried at a temperature of about 60 ° C. to 110 ° C., followed by a temperature of 500 ° C. to 800 ° C. under a reducing atmosphere. By firing for about 0.5 to 6 hours, the process of activating the introduced metal nanoparticles can be further carried out.
  • Rice husk, bamboo charcoal, and coal pitch (SP 115 ° C.) were crushed with a grinder, respectively, and classified into a sieve having a size of 80 mesh, and then 80 mesh passages were used as raw materials.
  • Each of the ground powders was mixed in the composition shown in Table 1 below, and then nitrobenzene (JUNSEI Chemical A, 99.5%) was added in an amount of 10% by weight relative to the pitch of coal as a modifier and mixed for about 2 hours.
  • sodium aluminate (NaAlO 2 ) prepared by reacting sodium hydroxide (NaOH) and aluminum hydroxide (Al (OH) 3 ) in an aqueous solution containing a surfactant as a colloiding agent was gradually added, and the colloidation reaction proceeded. I was.
  • the amount of aluminum hydroxide and sodium hydroxide used in consideration of the composition of the raw material, the molar ratio (SiO 2 / Al 2 O 3 ) of silica (SiO 2 ) and aluminum oxide (Al 2 O 3 ) to be produced by the gelatinization ) Is 5, the molar ratio of sodium oxide (Na 2 O) and silica (SiO 2 ) (Na 2 O / SiO 2 ) is 1.52, and the solvent (H 2 O) used to prepare sodium aluminate The molar ratio of sodium oxide (NaO 2 ) (H 2 O / Na 2 O) was adjusted to 28 to add.
  • the water content in the reaction system during the gelatinization reaction is adjusted to about 40% by weight relative to the solid content of the reaction material, aged for 2 hours at a temperature of 40 °C, 5L flow share mixer (manufactured by Lodige, Germany) Granules were granulated for 20 minutes to obtain a granular composition having an average particle diameter of 2.8 mm.
  • the dried extrudate was put into a rotary batch firing furnace (manufactured by Korean Ceramics) in an oxygen atmosphere, and reacted at 350 ° C. for 6 hours to insolubilize the low boiling point material generated during pyrolysis.
  • the insolubilized composition was then carbonized for 2 hours by heating to 600 ° C. in a rotary kiln, and activated at 850 ° C. for 2 hours while introducing water vapor at 1.5 times the solids.
  • an aqueous 5% by weight sodium hydroxide solution was added to the activated granular composition at a weight ratio of 1: 1, and aged at a temperature of 25 ° C. for 4 hours, followed by hydrothermal treatment for 8 hours by raising the temperature to 100 ° C.
  • hydrothermal treatment was performed at 250 ° C. for 8 hours.).
  • the mixture was washed with distilled water sufficiently and then dried at 110 ° C. for 3 hours.
  • Examples 1 to 5 of the raw material content and the type of grown zeolites are as shown in Table 1 below.
  • the prepared metal nanoparticle adsorption micelle solution was diluted to concentrations of 300 ppm, 500 ppm, 1000 ppm and 5000 ppm to prepare 1 L of a solution. Thereafter, 1 Kg of the adsorbent prepared in Example 2 was immersed, and then dried in a reflux drying oven for 6 hours at a temperature of 80 ° C. And after further baking for 4 hours at the temperature of 600 degreeC under reducing atmosphere (nitrogen), it cooled. Thereafter, the prepared adsorbent was pulverized with a grinder, and an adsorbent having a particle size of 40 to 60 mesh was used for performance evaluation.
  • the palm shell was heat-treated at 800 ° C. for 5 hours, and then activated at the weight ratio of 1.5 times the weight of the palm shell heat-treated at 950 ° C. while activating for 3 hours to prepare palm-aqueous activated carbon.
  • the activated carbon was ground to a particle size of 12 to 30 mesh using a mill to prepare an adsorbent.
  • bamboo was heat-treated at a temperature of 1000 ° C. for 5 hours to prepare bamboo charcoal, which was activated under a reducing atmosphere at a temperature of 850 ° C. while adding water vapor 1.5 times the weight of the char, for 3 hours. Subsequently, the activated bamboo activated carbon was ground to a particle size of 40 mesh to 60 mesh to prepare an adsorbent.
  • Example 2 Thereafter, the dried mixture was carbonized and activated in the same manner as in Example 1. Thereafter, 348 g of an aqueous sodium hydroxide solution (concentration: 4.2 wt%) was added thereto, and aged at a temperature of 25 ° C. for 48 hours, and then heated to 100 ° C. and hydrothermally treated for 24 hours.
  • an aqueous sodium hydroxide solution concentration: 4.2 wt%
  • compositions and physical properties of the adsorbents prepared in Examples and Comparative Examples were evaluated, and are shown in Tables 2 and 3 below. Specifically, the measurement of specific surface area (BET), pore distribution and pore volume was performed with a Sorptonmatic 1990 instrument (manufactured by Thermo Electron, Italy), and SEM structure analysis was performed on the adsorbents prepared in Examples 2 to 4, 1 is shown. In addition, the apparent specific gravity was tested according to the test method specified in KS M 1802, iodine adsorption capacity.
  • the deodorizing effect was tested by the deodorizing force test method by the Batch Test method. Specifically, a predetermined amount of hydrogen sulfide (H 2 S), ammonia (NH 3 ), and trimethyl amine ((CH 3 ) 3 N), which are deodorizing target substances, were respectively added to a 5 L container, and the mixture was stirred and stirred with 0.5 g of the sample. The change in concentration of the deodorizing subject matter was measured. At this time, the measurement equipment used GC and HEWLETT5890 SERIES II PLUS and the results are shown in Table 4 below.
  • H 2 S hydrogen sulfide
  • NH 3 ammonia
  • (CH 3 ) 3 N) trimethyl amine
  • Example 7 The adsorbent of Example 7 and the control test solution (sterile physiological saline) were each put in a sterile container, and the pre-cultured test bacteria were inoculated respectively. 5 and 10 minutes after inoculation, a certain amount is taken from the test solution and the control test solution to check the number of regenerated bacteria.
  • the bactericidal power was expressed as a percentage according to the following formula.
  • Test strains Escherichia Coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Almonella thyphimurium (KCTC 1925)
  • the peak area and concentration were detected by first flowing 109.5 ppm of standard ethylene gas into the adsorption column at a rate of 50 ml / min through MASS FLOW Control v / v. Thereafter, 5 g of sample was charged to the adsorption column, and standard ethylene gas was passed through the column filled with 5 g of sample at a rate of 50 ml / min. Thereafter, the numerical value was analyzed at intervals of 5 minutes through the automatic GC v / v, and the amount of adsorption was calculated according to the following equation and is shown in Table 6 below.
  • Ethylene Adsorption Flow Rate (ml / min) ⁇ Ethylene Concentration (mg / 1000ml) ⁇ Break-point time (min) ⁇ Sample Volume (g)
  • Example 7 The adsorbent of Example 7 was placed in a non-woven fabric (7 cm ⁇ 6 cm) in 5 g units, heat-sealed, and placed in a box, followed by freshness test under normal temperature (test conditions: normal temperature (20 ° C. to 30 ° C.), relative humidity 75% to 95 ° C. %, Retention time: 15 days) and the results are shown in Tables 7 to 10 below.
  • the fruits and vegetables treated with the adsorbent according to the present invention remained excellent freshness, especially vegetables and pears, such as cucumbers, broccoli, pumpkin or eggplant, apples, sensitive to ethylene reaction, apples Also, fruit such as kiwi or orange was found to have an excellent freshness maintaining effect, especially when the temperature was maintained at 10 °C it was confirmed that the freshness is more excellent.
  • the adsorbent of the present invention can simultaneously perform chemical and physical adsorption, and has excellent adsorption properties for lipophilic and hydrophilic substances, effectively removing ethylene, a mature decaying hormone, such as fruits, vegetables and other horticultural crops, It exhibits a bactericidal effect and can maintain excellent freshness of fruits and the like.

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Abstract

La présente invention concerne un agent adsorbant et son procédé de production, et plus spécifiquement, l'invention concerne un agent adsorbant comprenant une matrice contenant un corps de structure en carbone poreux présentant une structure cyclique dans un état constituant un agencement stratifié, et une céramique présente dans les pores du corps de structure en carbone poreux susmentionné. L'agent adsorbant de la présente invention peut simultanément présenter une adsorption chimique et physique, il présente des caractéristiques d'adsorption remarquables par rapport à des substances lipophiles et hydrophiles, il élimine efficacement l'éthylène qui est une hormone de mûrissement et de putréfaction pour, à titre d'exemple, les fruits, les légumes et autres plantes horticoles, il présente un effet antimicrobien et microbicide et il présente une remarquable capacité à maintenir la fraîcheur de fruits et analogues.
PCT/KR2009/000008 2008-01-02 2009-01-02 Agent adsorbant et son procédé de production WO2009084936A2 (fr)

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KR10-2008-0000196 2008-01-02

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CN114369729A (zh) * 2021-12-28 2022-04-19 江苏容汇通用锂业股份有限公司 一种利用锂矿渣进行浸出液除钾的工艺
US11325111B2 (en) * 2016-06-10 2022-05-10 Exxonmobil Research & Engineering Company Catalysts and methods of making the same

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KR102035867B1 (ko) * 2012-11-23 2019-10-24 서강대학교산학협력단 기공 내 요오드 또는 브롬이 포집된 요오드 또는 브롬 함유 제올라이트 복합체 및 이의 용도

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KR20090074420A (ko) * 2008-01-02 2009-07-07 주식회사 카보텍 담배 필터용 나노 흡착제 및 그의 제조방법

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WO2006103404A1 (fr) * 2005-03-29 2006-10-05 British American Tobacco (Investments) Limited Materiaux carbones poreux, articles a fumer et filtres a fumee utilisables dans ces articles, incorporant de tels materiaux
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KR20090074420A (ko) * 2008-01-02 2009-07-07 주식회사 카보텍 담배 필터용 나노 흡착제 및 그의 제조방법

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US11325111B2 (en) * 2016-06-10 2022-05-10 Exxonmobil Research & Engineering Company Catalysts and methods of making the same
CN114369729A (zh) * 2021-12-28 2022-04-19 江苏容汇通用锂业股份有限公司 一种利用锂矿渣进行浸出液除钾的工艺
CN114369729B (zh) * 2021-12-28 2023-11-03 江苏容汇通用锂业股份有限公司 一种利用锂矿渣进行浸出液除钾的工艺

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