KR101752967B1 - Pellet-producing apparatus for pelletizing a composition for ignition resistant molded-composite adsorbent comprising activated carbon and zeolite - Google Patents
Pellet-producing apparatus for pelletizing a composition for ignition resistant molded-composite adsorbent comprising activated carbon and zeolite Download PDFInfo
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- KR101752967B1 KR101752967B1 KR1020150124518A KR20150124518A KR101752967B1 KR 101752967 B1 KR101752967 B1 KR 101752967B1 KR 1020150124518 A KR1020150124518 A KR 1020150124518A KR 20150124518 A KR20150124518 A KR 20150124518A KR 101752967 B1 KR101752967 B1 KR 101752967B1
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- 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
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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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
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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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
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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
- B01J20/28—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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
Abstract
The process for preparing a zeolite / activated carbon composite composite adsorbent of the present invention comprises the steps of: a) preparing a pellet from a composition comprising a) a binder and a solvent selected from activated carbon, zeolite, phenolic resin, starch or sugars, b) Carbonization step, and c) pore activation step.
Also, the method for producing a molded composite adsorbent according to the present invention can provide a method for producing a composite adsorbent having improved specific surface area and strength, and can further improve the ignitability.
Description
The present invention relates to a method for producing a molded composite adsorbent of zeolite / activated carbon improved in ignitability, and more particularly to a method for producing a shaped composite adsorbent of zeolite / activated carbon in which the specific surface area is improved and the strength is increased to increase the ignitability will be.
Generally, adsorbents and catalyst materials used in adsorption and chemical reactions are mostly in the form of very fine porous powders in the range of 0.1 to 10 μm, and because of the problem of scattering, they can not be used as powders themselves, Spheroidal, tablet or the like having a particle size of from about 1 mm to about several mm and then used in the form of a pellet.
The formed catalyst and the adsorbents are mainly used after they are filled in a packing tower such as a reactor or an adsorption tower, and the performance of the catalyst and the adsorbent can be properly maintained only when they are filled in the packing tower at a uniform density. Accordingly, in order to uniformly fill the filling material in the filling tower, the size and shape of the filling material must be uniform, and as the shape of the filling material becomes closer to the spherical shape, not only the filling rate is increased but also the filling density is uniform and channeling phenomenon occurs . Therefore, spherical particles having a uniform particle size among various particle types are preferred.
However, most of inorganic fine powder materials have a thixotropic and viscous property, which makes it difficult to form a spherical shape. Due to the difficulties described above, spherical shapes are used with special equipment using rotation such as a fluidized bed granulator, a pan rounder, and a cone rounder (US Pat. No. 5,284,678).
Nevertheless, the semicircular sphering method using the above rotation takes a long time, the generation of the fine particles due to the unbound particles is increased, and the strength becomes weak. When the sphericity of a large amount is simultaneously made, the shape of the sphere is distorted And the distribution of the particle diameter is wide.
Accordingly, the present invention provides a method for producing a molded composite adsorbent of zeolite / activated carbon having a uniform particle size, wherein the strength of the composite adsorbent formed by the molding is at least 3 kg / cm 2, It is possible to provide a molded composite adsorbent having a high surface area and a function capable of reducing environmental pollution.
The present invention provides a method for producing a molded composite adsorbent of zeolite / activated carbon with improved ignitability.
The present invention also provides a composition applied to the production method of the present invention.
The present invention also provides a pelletizing apparatus for pelletizing a composition of the present invention into a pelletizing apparatus.
The present invention provides a method for producing a molded composite adsorbent of zeolite / activated carbon having improved ignitability, specific surface area, and strength, and an apparatus for producing a pellet of the composition of the present invention,
The process for preparing a zeolite / activated carbon composite composite adsorbent of the present invention comprises the steps of: a) preparing a pellet made from a composition comprising a) activated carbon, zeolite, a phenolic resin, and a binder and a solvent selected from starches or sugars, b) And c) pore activation of the carbonized pellets.
In the production method according to an embodiment of the present invention, the composition is not particularly limited to achieve the object of the present invention, but it is preferable that the composition contains 5 to 20 parts by weight of zeolite, 10 to 50 parts by weight of a phenol resin, From 2 to 15 parts by weight of one or more binders selected from the group consisting of polyvinyl alcohol and polyvinyl alcohol.
In the production method according to an embodiment of the present invention, the pore activation step may be manufactured by a pore activation method by carbon dioxide activation at 800 to 1100 ° C, although the method is not limited to attaining the object of the present invention.
In the production method according to an embodiment of the present invention, the shaped composite adsorbent may have a specific surface area of 900 to 2000 m 2 / g measured according to the BET method, but the present invention is not limited thereto.
In the production method according to an embodiment of the present invention, the molded composite adsorbent may have an average particle diameter of 1 to 10 mm, but the present invention is not limited to an average particle diameter of the composite adsorbent.
In the production method according to an embodiment of the present invention, the strength of the molded composite adsorbent is not less than 3 kg / cm 2 and can be manufactured as a non-limiting example of pellets having a strength of 3 to 8 kg / cm 2.
In the production method according to an embodiment of the present invention, the molded composite adsorbent has an ignition temperature of 450 to 600 ° C, which may be more effective in terms of improving the ignitability of the present invention.
In the manufacturing method according to an embodiment of the present invention, the molded composite adsorbent may have an effect of increasing the hydrogen sulfide removal rate.
Also, a molded composite adsorbent of zeolite / activated carbon prepared by the above-described production method of the present invention and an apparatus for producing the same may also be disclosed.
In an apparatus for producing pellets according to an embodiment of the present invention, the apparatus for producing pellets is a pelletizing apparatus for pelletizing the above-described composition by feeding it into a pelletizing apparatus. A drawer-type cartridge positioned above the cartridge base and having an upper surface opened in a height direction; A forming mold body located on top of the drawer type cartridge for pressing the composition contained in the cartridge; And a shaker located at a lower portion of the drawer cartridge and pelletizing the composition drawn from the cartridge, wherein the composition is dispensed when the cartridge is positioned on top of the cartridge support, The molding mold body is pressed and the composition can be drawn into the shaker in the form of a rod or a pellet through the lower end of the cartridge in which the plurality of holes are formed.
In the apparatus for producing pellets according to an embodiment of the present invention, the shaker may include a sieve for separating the drawn composition.
In the apparatus for producing a pellet according to an embodiment of the present invention, the sieve has a size of 1 to 10 mesh, and is shaken at a speed of 40 to 60 times / minute for 10 to 20 minutes, Lt; 0 > C.
The method for producing a molded composite adsorbent according to the present invention can provide a method for producing an adsorbent having improved specific surface area and strength. In particular, the molded composite adsorbent according to the present invention can be expected to have an effect of greatly improving the ignitability.
Further, the present invention can effectively provide a mass production system or a process of a functional composite molded product by providing a technology for developing and producing a high-quality clean component material.
Further, the composite adsorbent produced by the production method of the present invention can effectively remove the volatile organic compounds emitted by the use of fossil fuels, and can provide an adsorbent capable of operating in an environment rich in fire, ignition and explosion at high temperature and high pressure can do.
In addition, the apparatus for producing pellets of the present invention is capable of providing an effect of improving the strength of a composite adsorbent because of less generation of fine particles due to unattached particles, and at the same time, it is possible to provide a large amount of pellets having a specific shape, There is an advantage that can be provided.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a method for producing a molded composite adsorbent according to Examples 1 to 3 of the present invention. FIG.
2 is an XRD graph of a molded composite adsorbent according to Examples 1 to 3 of the present invention.
3 is a SEM photograph of a molded composite adsorbent according to Examples 1 to 3 of the present invention.
4 is a schematic view showing an apparatus for producing pellets according to an embodiment of the present invention.
Hereinafter, a method for producing a shaped composite adsorbent of zeolite / activated carbon with improved ignitability will be described in detail. The following embodiments and drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. In addition, unless otherwise defined in the technical and scientific terms used herein, unless otherwise defined, the meaning of what is commonly understood by one of ordinary skill in the art to which this invention belongs is as follows, A description of known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted.
The present invention provides a method for producing a molded composite adsorbent of zeolite / activated carbon, wherein the specific surface area is improved, the strength is improved, and the ignition temperature is significantly increased.
The process for preparing a zeolite / activated carbon composite composite adsorbent of the present invention comprises the steps of: a) preparing a pellet made from a composition comprising a) activated carbon, zeolite, a phenolic resin, and a binder and a solvent selected from starches or sugars, b) C) a pore activation step.
The carbonization step may be heat treatment or carbonization in a non-oxidizing condition, that is, in an inert gas atmosphere. Further, in the case of carbonization under the above conditions, it is further expected that the composite adsorbent of the present invention has improved ignitability, re-formed pores, and increased specific surface area.
The pore activation step may be performed by a carbon reduction reaction at 800 to 1100 ° C in a carbon dioxide atmosphere. That is, the present invention is characterized in that the surface of the composite adsorbent clogged with carbon or the composition described above is reacted with carbon dioxide after the carbonization step b) by carrying out a pore activation step in which the carbonization is carried out, and the specific surface area, Can be improved.
Further, the shaped composite adsorbent of zeolite / activated carbon of the present invention can be greatly improved to have a specific surface area of 900 to 2000 m < 2 > / g by carrying out the above-described a) pellet preparation step, b) carbonization step and c) pore activation step have. It is a matter of course that the specific surface area can be measured by a known BET method.
In addition, the average particle size of the composite adsorbent prepared by the above method may be 1 to 10 mm. Although not particularly limited, the average particle size of 3 to 7 mm can be better in terms of particle uniformity. In addition, if the shape of the composite adsorbent is spherical, it is better in terms of applicability and strength, but the present invention is not limited to the shape of the composite adsorbent.
In addition, the strength of the composite adsorbent prepared by the above method may be 3 to 8 kg / cm 2. That is, when the composite adsorbent of the present invention is manufactured within a range of the above strength and applied to a product having various functions, its external shape is maintained as it is, so that the ignitability and the pollutant adsorption characteristics of the present invention can be maintained.
Furthermore, the composite adsorbent produced by the above method has improved ignitability and can be characterized by an ignition temperature of 450 to 600 ° C. As used herein, the term " ignitability "means a property in which the fire does not easily occur or burns under a natural condition or in the presence of volatile and pyrophoric vapors at a constant temperature, and the ignitability is high. .
In addition, the composite adsorbent according to the present invention may have a hydrogen sulfide removal rate of 2 to 3%. This can be evaluated as the most important item in the evaluation of the functionality of the adsorbent. The composite adsorbent of the present invention has a hydrogen sulfide removal rate within the above range, and thus can be applied to the removal of environmental pollutants such as sulfur compounds contained in exhaust gas There is an advantage.
In addition, refineries and natural gas processing plants mainly use alkanolamine process, Claus off-gas process, Shell Claus off-gastreatment process, Stretford process process has been used to remove hydrogen sulfide in the gas. However, since most of these physicochemical desulfurization processes are operated at a high temperature / high pressure, there is a disadvantage in that a large amount of waste such as sulfurous acid gas or waste catalyst, which is a secondary pollutant, is generated.
Accordingly, in order to remove hydrogen sulfide generated at a high temperature, there arises a problem of using a material having high ignitability. The molded composite adsorbent of zeolite / activated carbon produced by the production method of the present invention has an advantage that it can be operated at the high temperature / high pressure by improving the ignitability.
The present inventors have long been devoted to the type, composition and manufacturing method of composite adsorbents for developing molded composite adsorbents having improved ignitability. Particularly, when the composite adsorbent is aggregated, its size is controlled to 1 to 10 mm, and when the components contained in the composite adsorbent are mixed at a specific ratio, the specific surface area is improved and the strength is improved And discovered a manufacturing method, and filed it.
In general, activated carbon is one of the carbon-based adsorbents, and has well-developed pores in the particles, and has excellent adsorption power, chemical resistance and heat resistance, and is widely used for liquid phase and vapor phase adsorption. Activated carbon can be produced by carbonizing and activating raw materials. Most of the non-carbon elements in the carbonization process are pyrolyzed and removed, and the carbides formed are slightly non-uniform dark-colored crystals and the development of the pore structure is negligible. Activation removes unorganized carbon compounds, creating interstitial spaces and removing some of the carbon in the crystals. In addition, pores can be generated by selectively oxidizing between the fine crystals and the surface of the microcrystals.
The pore structure of the activated carbon can be changed according to the raw material, the activation process, and the degree of activation, and the use of the activated carbon is determined according to the pore size. That is, the activated carbon having micropore developed is suitable for adsorption or molecular sieve of gas and vapor, and the activated carbon having well developed mesopore and macropore is suited for adsorption of solute from solution. However, although the pore size ratio can be controlled to some extent by the activation process, it is practically difficult to raise the meso and macropore at a certain level because the mechanical strength is lowered when the burn-off is too large.
In addition, the adsorption capacity of activated carbon can be varied depending on the surface and chemical properties as well as the pore structure. The surface of activated carbon is mainly composed of basal plane, and on the side of microcrystals is the edge of graphite surface. The basal plane is comparatively uniform in nature and does not have a functional group. The adsorption on this surface is mainly due to the van der Waals binding force, and a small amount of adsorption due to the action of π electrons may be added due to the chemical nature of the adsorptive. The surface of microcrystalline cores is composed of various functional groups and can exhibit non-uniform properties. If the equivalent is unsaturated, or if there is an unpaired electron or an atom other than carbon, the adsorption capacity of the activated carbon is changed, especially in polar molecules. The surface area represented by the functional group in the total surface area is a part but the adsorption ability can be remarkably changed by a change in the chemical property of a small size. The properties of the functional groups can be greatly affected by the activation method, raw materials, and the like. Activated carbon prepared at 400 to 500 ° C or less contains an acidic surface oxide, and the activated carbon produced at about 800 to 1000 ° C mainly contains a basic surface oxide. The two surface oxides may exhibit polarity.
Activated carbon has been used in a wide range of fields such as organic solvent recovery, deodorization, toxic gas removal, gas separation, water treatment, decolorization, medical use, electrode material, and catalyst coating due to its advantages such as meat porosity, heat resistance and chemical resistance. Since activated pores are highly developed in pores, they adsorb to the surrounding gas or liquid, generate heat, and are exothermic to oxidize and ignite in many cases.
In particular, Volatile Organic Compounds (VOCs) are substances that are the main factors of air pollution in addition to NO x and SO x in the exhaust gas. Most of them are chemical plants, pharmaceutical plants, and general All are emitted from industry.
However, activated carbon does not explode as a solid, but if it absorbs organic vapor to some extent, it explodes in dispersed state. This is because a dust explosion gives rise to thermal energy on the particle surface, and the surface temperature rises, causing molecules from the particle surface to undergo pyrolysis or a gasification action to form a combustible gas mixture with ambient air, and ignite and explode.
Therefore, it is very important to develop a composite adsorbent which increases the ignitability so as not to cause such ignition. The composite adsorbent according to the present invention exhibits the function of a new composite adsorbent which greatly improves the adsorption efficiency, strength and ignitability.
FIG. 1 is a schematic view illustrating a method of manufacturing a composite adsorbent according to an embodiment of the present invention. Referring to FIG. 1, a composite adsorbent according to an exemplary embodiment of the present invention, The manufacturing method may include a pellet preparation step (S100) in which the mixture is selected and a pellet is prepared from a composition including a binder and a solvent, a carbonization step (S200) in which the produced pellet is fired, and a pore activation step (S300) have.
In detail, the mixture of the pellet preparation step (S100) may be selected from activated carbon, zeolite, phenolic resin, and starch or saccharides.
That is, the activated carbon is one kind of carbonaceous powder and may have an average particle size of 100 to 400 mesh, but the present invention is not limited thereto.
The carbonaceous powder may be produced by using charcoal such as wood charcoal, crustacean charcoal, chaff charcoal or charcoal charcoal. In the production process according to the present invention, there is a carbonization step and a pore activation step. , Or a type of organic material that can be carbonized may be used.
In addition, the zeolite may be a mineral in which nano pores having a size of about 3 to 10 Å, which are capable of entering and exiting from feldspar, are arranged in a regular order. Such feldspar may be a two-dimensional and / or three-dimensional polyaluminosilicate, but is not limited thereto.
In describing the present invention, the zeolite may include at least one or more structures of zeolite A, ZSM-5, zeolite-X, zeolite-Y and zeolite-L.
Particularly, since zeolite is added to the composite adsorbent of the present invention, it is possible to expand the basic properties of the activated carbon, that is, the pore size distribution and the specific surface area, and further contributes to the improvement in ignition resistance. It is important.
In one preferred embodiment, the zeolite is not particularly limited, but may be 5 to 20 parts by weight, preferably 6 to 15 parts by weight, more preferably 8 to 15 parts by weight, based on 100 parts by weight of activated carbon, The specific surface area of the present invention can be improved and the ignitability can be further improved.
In addition, the above-mentioned saccharides may include a sugar selected from at least one of monosaccharides, glucose, fructose, galactose and the like. Further, the sugar can be used as sugar in a granulated state.
Specifically, the saccharide serves as a stabilizer for maintaining a spherical stable shape, a zeolite having a hydrophilic property and an active carbon having a hydrophobic property to be dispersed evenly or to be aggregated or coagulated. In the heat treatment process, It is possible to expect the role of additional pore formation in the interlayer.
In addition, the shaped composite adsorbent of zeolite / activated carbon prepared by the binder selected from the saccharides or starches of the present invention may serve to reduce cracks on the surface and inside thereof. This is a decrease in crack due to the glassfication of the sugar, and it can increase the strength of the composite adsorbent.
In one preferred embodiment, the binder selected from the starch or the saccharide may be used in an amount of 2 to 15 parts by weight based on 100 parts by weight of the activated carbon to improve vitrification and strength of the sugar.
The above-mentioned phenol resin may be a novolak-type solid phenol resin. As an example of the content of the preferable phenolic resin, the phenolic resin may be used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the activated carbon. When the phenol resin is used in the above range, the cohesive force of the composite adsorbent is weakened and there is no problem of cracking in the stirring process, and the shape thereof can be maintained during the shaking process so that sphering or agglomeration can be performed well.
In addition, in order to increase the pore ratio in the fine particle in the specific surface area characteristic of the composite adsorbent of the present invention, the thermal property of the phenol resin used for producing activated carbon is important. That is, the phenolic resin is greatly affected by the formation of pores between the fine particles by heat treatment such as curing, carbonization and activation. Thus, the addition of such a phenolic resin is indispensable to produce activated carbon having a high proportion of pores in the microparticles.
The present invention can also include the above-mentioned solvents. The solvent may be a lower alcohol having 1 to 4 carbon atoms, which is added and kneaded to impart molding and fluidity to a mixture comprising activated carbon, zeolite, phenolic resin, starch or saccharides.
In one preferred embodiment, the composition of the pelletizing step (S100) is prepared by mixing with the above mixture and solvent, and then the pellet may be prepared. The solvent may be used in an amount of 10 to 80 parts by weight based on 100 parts by weight of the activated carbon. When the solvent is used in the above range, the fluidity of the mixed composition is improved and molding can be performed well.
In the method for producing a composite adsorbent according to an embodiment of the present invention, the step (S100) of producing a pellet produced from the composition described above comprises: spraying and kneading a solvent on the mixture for 1 to 100 minutes to prepare a slurry; The slurry was pelletized Into an extruder to be formed, and extruding the extruded product; And drying and shaking the extruded pellet at 70 to 90 DEG C to produce a molded pellet.
Specifically, the extruding step may be performed by injecting 90 to 150 g of the slurry into a plurality of columnar forming molds of short length, and then pressing the mold at 0.1 to 10 kgf / cm2 using a press to form columnar or columnar pellets , Which is a step preceding to facilitate the production of the molded composite adsorbent according to the present invention.
Further, the extruded pellets may be drawn into a shaker to perform a shaking process. The shaking may mean moving repeatedly along the x and y axes.
More specifically, the shaker may comprise a sieve of 1 to 10 mesh. Also, the shaking process can be carried out at a speed of 40 to 60 times / minute on the body, shaking for 10 to 20 minutes, and simultaneous molding with hot air at 70 to 90 ° C.
In the method for producing a composite adsorbent according to an embodiment of the present invention, the carbonization step (S200) for firing the pellet of FIG. 1 is performed in an inert gas containing at least one of argon gas, helium gas, and nitrogen gas And the atmosphere of nitrogen gas may be particularly good for pyrolysis and carbonization reaction of the pellets.
In detail, the pyrolysis and carbonization reaction of the pellets are pyrolysis and carbonization reactions caused by phenol resin or saccharides and starch contained in the pellets. In addition, pyrolysis and carbonization reactions of the composite adsorbent of the present invention increase the pyrolysis temperature, Of the total number of respondents.
The heat treatment in the carbonization step (S200) may be performed at 400 to 600 ° C. The temperature of the heat treatment may be in the range of 450 to 550 캜. However, the temperature is not limited as long as the composite adsorbent of the present invention is pyrolyzed and carbonized. In addition, when the heat treatment temperature in the carbonization step (S200) is within the above range, the aforementioned pyrolysis and carbonization are sufficiently performed and the carbon content is increased.
As a specific, non-limiting example, the heat treatment temperature of the carbonization step S200 according to an embodiment of the present invention may be 400 to 600 ° C, and the heat treatment time may be 10 to 600 minutes.
In the method of producing a composite adsorbent according to an embodiment of the present invention, the pore activation step (S300) of the carbonized pellet of FIG. 1 may be heat-treated in an atmosphere containing carbon dioxide.
The heat treatment temperature of the pore activation step (S300) may be 800 to 1100 ° C. More preferably, the heat treatment temperature may be 900 to 1000 ° C, but is not limited to a temperature at which the composite adsorbent of the present invention is activated at pore.
When the heat treatment temperature in the pore activation step (S300) is within the above range, sufficient activation of pores can be achieved and the specific surface area thereof can be increased, so that the ignitability of the present invention can be improved.
Accordingly, the heat treatment temperature of the pore activation step (S300) according to an embodiment of the present invention may be 800 to 1100 ° C, and the heat treatment time may be 10 to 600 minutes.
The flow rate of the carbon dioxide may be 10 to 500 mL / min, preferably 50 to 300 mL / min, more preferably 100 to 200 mL / min, but the present invention is not limited thereto.
In the method for producing a composite adsorbent according to an embodiment of the present invention, in order to maintain the shape of the composite adsorbent prepared from the composition described above more intensively, it is preferable that the pellet production step (S100) and the carbonization step (S200) And drying the pellets by agglomerating at 80 to 150 DEG C and drying the pellets. The drying time is not particularly limited, but may be 10 to 200 minutes.
Particularly, in the method of manufacturing a composite adsorbent according to an embodiment of the present invention, the composite adsorbent can greatly improve the ignitability according to the amount of the zeolite added. As a specific example, in the case of a composite adsorbent in which zeolite is added in an amount of 2 to 4 parts by weight with respect to the ignition temperature of a composite adsorbent to which no zeolite is added, the ignition temperature may be increased by 50 to 60%, and 11 to 13 parts by weight of zeolite , It can be improved by 75 to 85% compared with the ignition temperature of the unadopted composite adsorbent.
In the method of preparing a composite adsorbent according to an embodiment of the present invention, the composite adsorbent may have a specific surface area of 900 to 2000 m < 2 > / g as measured according to the BET method. Referring to the BET specific surface area of the composite adsorbent of Table 2 to be described below, the specific surface area of the composite adsorbent of the present invention does not change largely as the content of zeolite increases, but rather the carbonation step (S200) and the pore activation step (S300) It can be confirmed that the specific surface area is greatly improved through the process.
Although the specific surface area measurement of the composite adsorbent according to an embodiment of the present invention is not limited to achieving the object of the present invention, a specific measurement method uses an amount of low temperature nitrogen or liquefied nitrogen to adsorb them on the composite adsorbent And measuring the specific surface area, but the present invention is not limited thereto.
In addition, in the method for producing a composite adsorbent according to an embodiment of the present invention, the strength of the composite adsorbent may be 3 to 8 kg / cm 2. The strength may be specifically compressive strength and may be applied to products having various functions when the composite adsorbent of the present invention is produced within the range of the strength. As a specific example, the present invention can be applied to a wide range of fields such as organic solvent recovery, deodorization, toxic gas removal, gas separation, water treatment, decolorization, medical use, electrode material,
According to another embodiment of the present invention, a composite adsorbent produced according to the above-described production method can be provided. The composite adsorbent is capable of removing toxic gases such as ammonia, hydrogen sulfide, benzene, etc., has a bacterial reduction rate of 93% or more, and a mechanical strength of 3 to 8 kg / cm 2. In addition, the MEK ignition rate may be 0% and the autoignition temperature may be above 350 ° C.
The composite adsorbent may have a specific surface area of 900 to 2000 m < 2 > / g as measured according to the BET method.
The composite adsorbent may have an ignition temperature of 450 to 600 ° C.
The present invention also provides a pelletizing pelletizing apparatus for pelletizing a composition according to the above manufacturing method into a
Also, when the
In the apparatus for manufacturing a pellet according to an embodiment of the present invention, the
In the apparatus for producing pellets according to an embodiment of the present invention, the
In addition, in order to take a large amount of pellets or a molded product, there is a problem in that the molding die must be moved by using a power device or the like in the heavy forming
In addition, the
In detail, the
In a specific, non-limiting example, the
In addition, the
In addition, the
In the apparatus for producing a pellet according to an embodiment of the present invention, the
Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.
[Example 1]
, 72 g of activated carbon having a mean particle size of 300 mesh (nevien, Coal based actibated carbon), 4 g of zeolite (VALFOR-100 (Zeolite 4A)) and 20 g of phenol resin (Kangnam Hwasung, 1364K) , 2 g of sugar (sugar) and 2 g of starch were uniformly mixed and sprayed with 25 g of ethanol, followed by kneading.
The kneaded mixture was introduced into a molding mold for sphering as a slurry. The amount of slurry injected at this time was 110 g. The injected slurry was pressurized and extruded into pellets in a plurality of cylindrically shaped molds having a short length, and the pressure at this time was 3 kgf / cm 2.
Thereafter, the pellet was placed on a sieve of 7 mesh, and a spherical shaped body was produced by shaking with a hot air of 85 캜 in a shaker. At this time, the vibration speed was 50 times / min.
Thereafter, the molded pellets were dried in an air atmosphere at 100 DEG C for 1 hour.
The pellets thus produced were pyrolytically carbonized at 500 DEG C for 2 hours at a circulation rate of 150 mL / min. After pyrolytic carbonization, carbon dioxide gas was used at 950 ° C for activation for 2 hours at a feed rate of 150 mL / min to prepare a composite adsorbent. At this time, the temperature raising rate in the activation furnace was set to 10 ° C / min.
[Example 2]
Except that 70 g of activated carbon and 6 g of zeolite in Example 1 were mixed and mixed.
[Example 3]
Except that 68 g of activated carbon and 8 g of zeolite in Example 1 were mixed and mixed.
[Comparative Example 1]
Except that 76 g of activated carbon and zeolite were not added in Example 1.
Table 1 below shows the ignition temperatures according to the examples and comparative examples. As a result, it was found that the ignition temperature according to the embodiment of the present invention was increased to 490 ° C or higher, preferably to 568 ° C. Also, the MEK ignition rate was 0% in all of the above examples at 350 ° C or higher.
The measurement of the ignition temperature was carried out by the KS M 1820 measurement method of activated carbon ignition point. Alumina crucibles were used and the temperature was measured at a temperature rising rate of 10 ° C / min from room temperature to 600 ° C.
Table 2 shows the specific surface area according to the above embodiment. As a result, it was found that the specific surface area according to the embodiment of the present invention increases to 981 m 2 / g or more, preferably to 1193 m 2 / g.
The specific surface area was measured by a BET method using a specific surface area measuring apparatus (Quantachrom, Monosorb) using liquid nitrogen. The measurement sample was lowered to the temperature of the liquid nitrogen, and the adsorption amount of the nitrogen gas was measured and converted into the specific surface area.
Table 3 shows strength measurements according to the above examples. As a result, the strength according to the embodiment of the present invention was found to increase to 3.87 kg / cm 2, preferably to 4.89 kg / cm 2. It can be confirmed that the strength increase rate of Example 3 is improved by about 26% compared to Example 1. That is, it shows that the amount of zeolite greatly affects the strength of the present invention, and it can be confirmed that the addition of zeolite greatly affects the binding force and shape of the molded composite adsorbent.
The strength was measured according to JIS R 7212. Strength was measured at 1 point and the instrument used was Instron 4201, the support distance was 30 mm / min, and the cross head speed was 0.5 mm / min. The diameter of the specimen was measured with spherical particles of about 5 mm and the intensity was calculated by the following equation (1).
[Relation 1]
In the relational expression 1, σ F is the strength (kg / cm 2), P is the fracture load (kg), L is the support distance (cm), B is the sample width (cm), and D is the sample thickness (cm).
2 shows the results of the x-ray diffraction analysis according to the above embodiment. As shown in Fig. 2, () is the diffraction peak of activated carbon, and () is the diffraction peak of zeolite. From these results, the crystal structure of the composite adsorbent according to the embodiment of the present invention shows a mixed state of activated carbon and zeolite structure.
The x-ray diffraction analysis was performed in powder form using XRD (Shimata XD-D1, Japan).
FIG. 3 is a photograph of the fracture surface of the composite adsorbent of the present invention measured by SEM. As a result, the interface (or surface) of the activated carbon and the zeolite contained in the composite adsorbent could be confirmed clearly. In particular, it was further confirmed that the distribution of activated carbon, zeolite and binder was clearly distinguished in the case of the composite derived from the raw activated carbon. These properties are expected to affect the adsorption or pore properties, and mechanical strength properties, and will also affect the spheroidization of the pellets. In addition, the elements contained in the composite adsorbent of zeolite / activated carbon were analyzed based on the EDX bound to the SEM. Carbon (C), silicon (Si) and aluminum (Al) ) Were detected.
The SEM measurement method was measured using an SEM (JSM-5200, Japan). The magnification was fixed at 5,000 times and the acceleration voltage was measured at 20 kV. In addition, the composition of composite adsorbent was measured using EDX equipped with SEM.
Table 4 below shows the hydrogen sulfide gas removal rates according to the examples. As a result, it was found that the hydrogen sulfide removal rate according to the embodiment of the present invention is increased to 2.45% or more, preferably 2.68%. In other words, it can be seen that the composite adsorbent produced by the above example shows a change in the hydrogen sulfide removal rate in relation to the amount of zeolite, and this fact has a close relationship with the moldability and gas removal efficiency due to the influence of the granular zeolite on the moldability .
The hydrogen sulfide gas removal rate was measured by using 90% H 2 S 10% / N 2 as an H 2 S standard gas. The flow rate was 80 mL for 20 minutes, the column diameter was 15 mm, The amount of feed and the amount of later emission was measured and measured as the amount of adsorbed by the removal efficiency. At this time, the hydrogen sulfide removal rate means the% of hydrogen sulfide adsorbed on the adsorbent
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Those skilled in the art will recognize that many modifications and variations are possible in light of the above teachings.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
100: cartridge base, 110: pelletizer support
200: drawer type cartridge, 210: hole, 220: lever
300: Molding mold body, 310: Molding mold, 320: Molding mold support
400: shaker
500: Pelletizer
Claims (11)
A cartridge base;
A drawer-type cartridge positioned above the cartridge base and having an upper surface opened in a height direction;
A forming mold body located on top of the drawer type cartridge for pressing the composition contained in the cartridge; And
And a shaker located at a lower portion of the drawer type cartridge and pelletizing the composition drawn from the cartridge,
The composition is applied when the cartridge is positioned on the top of the cartridge pedestal, the molding mold body is pressed when the cartridge is drawn into the lower portion of the molding mold body,
Wherein the composition passes through a lower end of a cartridge having a plurality of holes and is drawn out into the shaker in the form of a rod or a pellet.
Wherein the shaker comprises a sieve for separating the drawn composition.
Characterized in that the sieve has a size of 1 to 10 mesh and is molded by applying hot air at 70 to 90 DEG C while shaking at a rate of 40 to 60 times per minute for 10 to 20 minutes. .
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| KR102051844B1 (en) | 2018-05-14 | 2019-12-05 | 주식회사 카본텍 | Air purification system using the activated carbon composite |
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