CN113546605A - Adsorbent material - Google Patents
Adsorbent material Download PDFInfo
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- CN113546605A CN113546605A CN202110392283.9A CN202110392283A CN113546605A CN 113546605 A CN113546605 A CN 113546605A CN 202110392283 A CN202110392283 A CN 202110392283A CN 113546605 A CN113546605 A CN 113546605A
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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
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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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
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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Abstract
The present invention addresses the problem of providing an adsorbent material having excellent adsorption performance and reduced elution of iron. The adsorbent contains porous carbide and iron, and the content of organic carbon in the carbide is 30% to 85%. The adsorbent contains porous carbide and iron and has a specific surface area of 100m2500m above/g2The ratio of the carbon atoms to the carbon atoms is less than g. The adsorbent contains porous carbide and iron, and has a total pore volume of 1000mm3More than g and 3000mm3In terms of/gThe following steps. The iron content of the adsorbent is 5% to 35%.
Description
Technical Field
The present invention relates to an adsorbent. In particular to an adsorbing material for adsorbing phosphorus.
Background
A technique of artificially recovering carbon dioxide and storing it underground in order to reduce the amount of carbon dioxide in the atmosphere is known. For example, biomass (biomass) such as wood or agricultural crops can absorb carbon dioxide in the atmosphere and fix the carbon dioxide as organic carbon to the biomass. However, since these biomasses are organic substances, they are decomposed and decomposed even if stored underground, and carbon dioxide is released into the atmosphere again. On the other hand, when the biomass is heated while blocking oxygen, oxygen atoms and hydrogen atoms are desorbed, and carbide composed of carbon components and ash components can be generated. Since the carbide is a carbon block containing no polysaccharide or amino acid decomposed by microorganisms, it is very stable in the environment (underground) and hardly decomposed. Carbonized biomass has been used in agricultural fields since ancient times, and is also recognized as a soil improving material in japanese law (soil improvement law), and therefore, by applying fertilizer to agricultural fields and the like, carbon dioxide can be sequestered and stored underground. In other words, agricultural utilization of the biomass carbides helps to reduce the amount of carbon dioxide in the atmosphere. However, given the cost required to produce carbide and current carbon pricing, the use of carbide only for soil reclamation is not matched by production costs.
On the other hand, since the carbide is porous, it is known that the surface area thereof is very large. By utilizing such a surface area, the carbide can be used as an adsorbent for various substances. For example, patent document 1 describes a phosphorus recovery material using calcium-supported carbide. By adsorbing phosphorus using such a phosphorus recovery material, water pollution caused by discharge of phosphorus into natural waters can be suppressed. Further, when the phosphorus recovery material having phosphorus adsorbed thereon is buried in a farm land, the crops can dissolve the phosphorus adsorbed on the phosphorus recovery material by the organic acid released from the roots. This phosphorus acts as a fertilizer for agricultural crops, and therefore, the yield of farmlands in which phosphorus-recovering materials are buried can be increased, or high-quality agricultural crops can be grown.
As described above, there is an increasing demand for carbides that can suppress environmental pollution by adsorbing a certain substance, or carbides that can apply such a harmful substance to other applications, in addition to improving soil properties of soil.
(Prior art document)
(patent document)
Patent document 1: japanese laid-open patent publication No. 2007-75706
Patent document 2: japanese patent laid-open No. 2020-11211
Disclosure of Invention
(problems to be solved by the invention)
However, in the phosphorus recovery material of patent document 1, it is necessary to use a material containing a large amount of silicon, such as rice husk or diatomaceous earth. In the case of using a material containing a large amount of silicon, the production amount of the phosphorus recovery material is limited. In addition, the allowable amount of substances such as phosphorus that can be adsorbed is limited.
Patent document 2 describes an adsorbent made of iron-containing carbide. Since the carbide has high conductivity, electrons can be rapidly exchanged between the carbide and iron attached to the carbide in the pores. Therefore, if an adsorbent composed of a carbide containing iron is put into water, iron is ionized to generate a hydroxide such as iron oxyhydroxide (FeOOH), and the hydroxide reacts with phosphoric acid ions present in water to form iron phosphate, which is adsorbed and fixed to the carbide. That is, the adsorbent composed of iron-containing carbide can efficiently adsorb phosphorus by the above mechanism.
On the other hand, if iron is eluted from the adsorbent, the adsorbed phosphorus is released, and therefore, it is required to reduce the elution of iron from the adsorbent.
One embodiment of the present invention has been made in view of the above problems, and an object thereof is to provide an adsorbent having excellent adsorption characteristics and reduced elution of iron.
(measures taken to solve the problems)
An adsorbent according to an embodiment of the present invention is composed of iron-containing carbide, and the content of organic carbon in the carbide is 30% to 85%.
The adsorbent according to one embodiment of the present invention contains porous carbide and iron, and has a specific surface area of 100m2500m above/g2The ratio of the carbon atoms to the carbon atoms is less than g.
The adsorbent according to one embodiment of the present invention contains porous carbide and iron, and has a total pore volume of 1000mm3More than g and 3000mm3The ratio of the carbon atoms to the carbon atoms is less than g.
The iron content may be 5% or more and 35% or less.
The content of organic carbon in the carbide may be 50% or more and 85% or less.
At least a part of the organic carbon may be generated by calcining at least one selected from molasses, waste molasses, starch, dextrin, corn starch, rice bran, polyvinyl alcohol, pulp waste liquor, lignosulfonate, carboxymethyl cellulose, hydroxypropyl methyl cellulose, Sodium alginate (Sodium alginate), phenolic resin, and tar pitch.
The adsorbent material may be substantially cylindrical in shape.
The amount of phosphorus adsorbed by the adsorbent may be 5mg-P/g or more.
(Effect of the invention)
The adsorbent according to one embodiment of the present invention has reduced elution of iron and excellent adsorption characteristics. Further, since the adsorbent can be produced without requiring a special production apparatus, the production cost of the adsorbent can be suppressed, and an inexpensive adsorbent can be provided.
Drawings
Fig. 1 shows a schematic view of an adsorbent material according to one embodiment of the present invention.
Fig. 2 is a flowchart showing a method for producing an adsorbent according to one embodiment of the present invention.
Fig. 3 is a diagram illustrating a method for producing an adsorbent according to one embodiment of the present invention.
(description of reference numerals)
10: adsorbing material; 20: granulating; 100: a first carbide; 110: iron;
120: a second carbide; 200: carbide; 210: an iron compound; 220: an organic binder.
Detailed Description
Hereinafter, an adsorbent and a method for producing an adsorbent according to one embodiment of the present invention will be described with reference to the drawings. However, the adsorbent and the method for producing the adsorbent in one embodiment of the present invention may be implemented in many different ways, and should not be construed as being limited to the description of the example shown below. In the drawings referred to in the present embodiment, the same reference numerals are given to the same parts or parts having the same functions, or letters are added to the same reference numerals, and overlapping descriptions are omitted.
[1. Structure of adsorbent 10 ]
The structure of the adsorbent 10 will be described with reference to fig. 1.
Fig. 1 is a schematic view of an adsorbent 10 according to one embodiment of the present invention. As shown in fig. 1, the adsorbent 10 includes a first carbide 100, iron 110, and a second carbide 120. In the adsorbent 10, the first carbide 100 and the second carbide 120 may be the same carbide or different carbides. Details will be described later, but the raw materials of the first carbides 100 and the second carbides 120 are different. Therefore, for convenience, the first carbide 100 and the second carbide 120 are described differently below based on the difference in raw materials.
The adsorbent material 10 has a so-called pellet (pellet) shape. Details will be described later, but the adsorbent 10 is granulated to be formed into a granular shape. The shape of the adsorbent 10 is, for example, a substantially cylindrical shape, a substantially elliptic cylindrical shape, a substantially polygonal columnar shape, or the like, but is not limited thereto.
The substantially cylindrical shape is preferably a right circular cylindrical shape, but is not limited thereto. The ratio (major axis/minor axis) of the major axis (major axis) to the minor axis (minor axis) of the substantially cylindrical circle is 1 to 5. On the other hand, a substantially cylindrical shape having a ratio of the major axis to the minor axis (major axis/minor axis) of more than 5 is defined as a substantially elliptical columnar shape. In addition, the substantially cylindrical facing surfaces may not have the same size. In addition, the substantially cylindrical shape in this specification includes a substantially cylindrical shape with a portion missing.
The substantially polygonal columnar shape includes, for example, a triangular columnar shape, a quadrangular columnar shape, a pentagonal columnar shape, a hexagonal columnar shape, and the like. The facing surfaces of the substantially polygonal columnar shape may not have the same size. In addition, the substantially polygonal columnar shape in the present specification includes a substantially polygonal columnar shape with a portion missing.
The shape of the adsorbent 10 is determined by the shape of the granulated substance 20 described later, but the height H (see fig. 1) of the adsorbent 10 is 1mm or more and 20mm or less, preferably 3mm or more and 15mm or less, and more preferably 6mm or more and 12mm or less. The long axis D (the maximum diameter in the direction perpendicular to the height, see fig. 1) of the adsorbent 10 is 1mm to 20mm, preferably 2mm to 10mm, and more preferably 3mm to 8 mm. The size of the adsorbent 10 may be controlled in the manufacturing process of the adsorbent 10. Therefore, the size of the adsorbent 10 is preferably within the above range that is easy to use and has a good adsorption effect.
The adsorbent 10 may be porous. That is, the first carbide 100 and the second carbide 120 may be porous. In the adsorbent 10, the iron 110 may be contained in the porous material of the first carbide 100 and the second carbide 120.
[2. method for producing adsorbent 10 ]
A method for producing the adsorbent 10 according to one embodiment of the present invention will be described with reference to fig. 2 and 3.
Fig. 2 is a flowchart illustrating a method for producing the adsorbent 10 according to one embodiment of the present invention. Fig. 3 is a diagram illustrating a method for producing the adsorbent 10 according to one embodiment of the present invention.
As shown in fig. 2, the method for producing the adsorbent 10 includes a mixing step (S110), a kneading step (S120), a granulating step (S130), and a calcining step (S140). Next, each process will be explained.
[2-1. mixing step (S110) ]
In the mixing step (S110), as shown in fig. 3 (a), the carbide 200 and the iron compound 210 are mixed.
The carbide 200 is, for example, charcoal, bamboo charcoal, white charcoal, black charcoal, wood charcoal, coconut charcoal, rice hull charcoal, powdered charcoal, or the like. The carbide 200 can be produced by carbonizing organic materials such as stumpage (including thinning woods such as broad-leaved trees, coniferous trees, and bamboos, and woodland wastes), wastes from wood-making plants or wood-processing plants (including sawdust, bark chips, and chips), plant shells, building demolition materials, and woody wastes from furniture.
Carbonization of an organic substance can be performed by heating the organic substance in an inert gas atmosphere such as nitrogen or argon, an oxygen-free atmosphere, a low-oxygen atmosphere, a reducing atmosphere, or a reduced-pressure atmosphere. When the carbonization of the organic material is carried out in a reduced pressure atmosphere, the carbonization temperature may be 10 DEG 2Pa is 10 or more5Low vacuum state of less than Pa, 10-1Pa is 10 or more2Vacuum state of less than Pa, 10-5Pa is 10 or more-1High vacuum state of Pa or less, or 10-5And is carried out in an ultra-high vacuum state of less than Pa. In the case where the carbonization of the organic material is performed in a low-oxygen atmosphere, the carbonization may be performed at an oxygen concentration of 0.01% to 3%, preferably 0.1% to 2%. The heating temperature for carbonizing the organic substance is 400 ℃ to 1200 ℃, preferably 500 ℃ to 1100 ℃, more preferably 600 ℃ to 1000 ℃, and particularly preferably 600 ℃ to 900 ℃. The heating time is 10 minutes to 10 days, preferably 10 minutes to 5 hours.
The carbonization of the organic substance can be performed by internal combustion or external heating using a batch-type open-type or closed-type kiln, a continuous rotary kiln, a swing-type carbonization furnace, a spiral furnace, a heating chamber, or a capped heat-resistant container (crucible). The internal heating type is a carbonization furnace which secures heat required for carbonization by a material and can carbonize an organic substance by supplying oxygen required for burning the material. The external heating type is a carbonization furnace which supplies heat required for carbonization from the outside and can perform carbonization of organic substances by blocking oxygen.
When the organic substance is heated under the reducing conditions, decomposition of the composition of the organic substance starts at the middle of the temperature rise (for example, about 280 ℃), oxygen or hydrogen in the organic substance volatilizes as a gas such as carbon dioxide, carbon monoxide, hydrogen, or hydrocarbon, and the organic substance changes to amorphous carbon having a large carbon content. Further heating at a high temperature further reduces oxygen or hydrogen in the organic matter, and carbide 200 composed of high-purity fixed carbon and ash is produced. Since moisture or a constituent in the organic material is desorbed as a volatile gas or the like, the carbide 200 generated by carbonization of the organic material becomes a porous material in which a large number of continuous pores having different sizes are formed. The carbide 200 formed by carbonization as the heating temperature rises has heat resistance (refractoriness), adsorbability, or electrical conductivity. Therefore, the carbide 200 may be porous, or may have heat resistance (refractoriness), adsorbability, or conductivity.
The iron compound 210 may be a divalent iron compound or a trivalent iron compound, and divalent and trivalent iron may be present in combination. As the iron compound 210, iron oxide, iron chloride, iron nitrate, iron sulfate, iron acetate, iron oxalate, or the like can be used. Among them, as the iron compound 210, iron oxide which is stable in performance and inexpensive is preferable. The iron oxide is, for example, FeO (wustite), Fe 2O3(hematite or maghemite) or Fe3O4(magnetite), and the like. Iron compound 210 may be a single compound or may contain multiple compounds.
In addition, a metal compound other than iron may be used instead of iron compound 210. As the metal other than iron, for example, aluminum, vanadium, nickel, cobalt, manganese, magnesium, calcium, or an alloy thereof can be used.
The carbides 200 generally contain water, and the content of water varies depending on the kind of the carbides 200. Therefore, the mixing ratio of the carbide 200 and the iron compound 210 is calculated based on the amount of the solid component of the carbide 200. For example, when 100g of the carbide 200 contains 5% of water, the amount of the solid content of the carbide 200 can be calculated as 100 × 0.95 — 95 (g).
The mixing ratio of the amount (α) of the solid component of the carbide 200 to the amount (β) of the iron compound is α: β 100: 1 to 80, preferably alpha: β 100: 10 to 50, more preferably α: β 100: 20 to 40. If the mixing ratio is within the above range, the carbide 200 and the iron compound 210 are not aggregated, and the carbide 200 and the iron compound 210 are uniformly mixed.
When the carbide 200 and the iron compound 210 are mixed, the respective particle diameters of the carbide 200 and the iron compound 210 may be adjusted. By adjusting the particle diameters of the carbide 200 and the iron compound 210, the carbide 200 and the iron compound 210 can be uniformly mixed. The particle size of each of the carbide 200 and the iron compound 210 can be adjusted by crushing the carbide 200 or the iron compound 210. In particular, since the grain size of carbide 200 is larger than that of iron compound 210 in many cases, carbide 200 may also be crushed so that the grain size of carbide 200 matches that of iron compound 210.
The carbide 200 and the iron compound 210 may be crushed in the later-described kneading step (S120), but fine adjustment of the particle size is difficult in the kneading step (S120). Therefore, when the grain sizes of the carbide 200 and the iron compound 210 are adjusted, it is preferable to adjust the grain sizes of the carbide 200 and the iron compound 210 in advance in the mixing step (S110).
The sizes of the carbide 200 and the iron compound 210 are not particularly limited, but the average particle size of the carbide 200 is preferably 1 μm or more and 50mm or less, the average particle size of the iron oxide is 1 μm or more and 10mm or less, more preferably the average particle size of the carbide 200 is 5 μm or more and 2mm or less, and the average particle size of the iron oxide is 1 μm or more and 1mm or less. When the sizes of the carbide 200 and the iron compound 210 are within the above ranges, not only the carbide 200 and the iron compound 210 can be uniformly mixed, but also the organic binder 220 can be attached to the surfaces of the carbide 200 and the iron compound 210, respectively, in a kneading step described later, to integrate the carbide 200 and the iron compound 210.
In the mixing of the carbide 200 and the iron compound 210, a certain amount of water may be added. By adding water, the carbide 200 and the iron compound 210 can be uniformly kneaded in the kneading step (S120) described later while preventing the generation of dust in the mixing step (S110).
In the mixing step (S110), a mixture of the carbide 200 and the iron compound 210 is produced.
[2-2. kneading step (S120) ]
In the kneading step (S120), as shown in fig. 3 (B), the organic binder 220 is added to the mixture (the carbide 200 and the iron compound 210) and kneaded to produce a paste (paste).
Examples of the organic binder 220 include molasses, starch, dextrin, corn starch, rice bran, polyvinyl alcohol, pulp waste liquid, lignosulfonate, carboxymethyl cellulose, hydroxypropyl methyl cellulose, sodium alginate, phenol resin, tar pitch, and the like. The organic adhesive 220 may contain one material or a plurality of materials. In particular, molasses or waste molasses is preferable as the organic binder 220. Molasses contains a large amount of solid components, and therefore the paste is easily solidified. Further, since the molasses contains a large amount of carbon components, the granulated substance can be efficiently reduced in the calcination step (S140) described later. Furthermore, molasses is inexpensive and contains few harmful components, so that the production cost of the adsorbent can be suppressed, and the produced adsorbent can be used as a safe fertilizer.
The viscosity of the organic adhesive 220 can be adjusted as necessary. For example, water or an organic solvent may be added to the organic binder 220 to adjust the viscosity of the organic binder 220. If the viscosity of the organic binder 220 is too high, kneading becomes difficult. Further, if the viscosity of the organic binder 220 is too low, the viscosity of the paste must be adjusted before the granulation step (S130) described later. The viscosity of the paste can be adjusted by evaporating the added water or organic solvent, but not only the step of evaporating the water or organic solvent is required, but also the carbide 200 and the iron compound 210 are aggregated by the evaporation of the water or organic solvent, and the dispersibility of the carbide 200 and the iron compound 210 in the organic binder 220 is lowered. Therefore, the viscosity of the organic binder 220 is preferably adjusted before mixing with the mixture.
The amount of the organic binder 220 added is based on the amount of the solid content of the carbide 200. The ratio of the amount of solid component (α) of the carbide 200 to the amount of solid component (γ) of the organic-based binder 220 is α: γ is 100: 10 to 1000, preferably alpha: γ is 100: 100 to 500, more preferably α: γ is 100: 100 to 300.
In the kneading step (S120), the parameters for determining the dispersibility of the carbide 200 and the iron compound 210 in the organic binder 220 are not limited to the mixing ratio of the mixture and the organic binder 220. The dispersibility in the mixing step (S110) can be controlled by parameters such as the mixing temperature and mixing time of the mixer. Therefore, the mixer will be explained below.
A mixer may be used to mix the mixture and the organic binder 220. Examples of the kneading machine include a single-screw kneading machine, a twin-screw kneading machine, a kneading roll (kneading roll), a kneader (kneader), and a banbury mixer.
A kneader having a mixing function may be used. In this case, the mixing step (S110) and the kneading step (S120) may be performed continuously. For example, the carbide 200 and the iron compound 210 are put into a mixer and mixed. Subsequently, the organic binder 220 is fed into a mixer and mixed with the mixture. The carbide 200, the iron compound 210, and the organic binder 220 may be collectively charged into a kneader and mixed and kneaded, but the carbide 200 and the iron compound 210 are likely to aggregate and bubbles are likely to be generated. Therefore, it is preferable to separately perform the mixing step (S110) and the kneading step (S120). In the kneading step (S120), a fixed amount of the organic binder 220 can be added to the mixture at a constant rate by using a kneader.
The kneading temperature may be arbitrarily set, but is 0 ℃ to 50 ℃, preferably 10 ℃ to 40 ℃. The kneading time is preferably 1 second to 1 hour, preferably 1 minute to 30 minutes, and more preferably 1 minute to 15 minutes. By setting the parameters of the kneading step (S120) within the above ranges, the dispersibility of the carbide 200 and the iron compound 210 in the organic binder 220 can be optimized.
In the above-described kneading step (S120), a paste in which the carbide 200 and the iron compound 210 are dispersed in the organic binder 220 is produced.
[2-3 ] granulation step (S130) ]
In the granulation step (S130), as shown in fig. 3 (C), the paste is granulated to produce granules 20 containing the carbide 200, the iron compound 210, and the organic binder 220.
A granulator may be used to produce the granulation 20. As the granulator, for example, a compression granulator, an extrusion granulator, a roll granulator, a blade granulator, a melt granulator, a spray granulator, or the like can be used. For the production of the substantially cylindrical granulation product 20, an extrusion type granulator is preferably used. Here, the production of the granulation mass 20 using an extrusion granulator will be described.
The extrusion granulator is extrusion-molded from a die (die) attached thereto into a paste having a predetermined shape. The extruded paste was cut into a predetermined length to produce a granulated substance 20 having a granular shape with the extrusion direction being the height direction. The length of the granulated material 20 (the height of the pellet shape) can be adjusted by adjusting the cutting speed (the rotational speed in the case of the rotary cutting method) of the extrusion granulator. Further, the axis (diameter when the cross-sectional shape is circular) of the granulated substance 20 can be adjusted by adjusting the opening diameter of the die. Therefore, by using the extrusion granulator, the granulated material 20 having a particle shape (for example, substantially cylindrical shape) with a controlled size can be produced.
The length of the granulated substance 20 is 1mm or more and 20mm or less, preferably 3mm or more and 15mm or less, and more preferably 6mm or more and 12mm or less. The diameter of the granulated substance 20 is 1mm or more and 20mm or less, preferably 2mm or more and 10mm or less, and more preferably 3mm or more and 8mm or less. If the size of the granulated substance 20 is within the above range, the iron compound 210 can be sufficiently reduced in the calcination step (S140), and therefore the adsorption effect of the adsorbent 10 can be improved.
The cross-sectional shape of the granules 20 is not limited to circular. The cross-sectional shape of the granulated substance can also be changed by changing the opening shape of the die. The cross-sectional shape of the granulated substance may be, for example, an ellipse or a polygon. That is, the granulated substance 20 may have a particle shape of not only a cylindrical shape but also an elliptic or polygonal cylinder shape.
In the granulating step (S130), an auxiliary agent may be added to stabilize the particle shape of the granulated substance 20. Examples of the auxiliary agent include organic resins such as polyester resins, acrylic resins, phenol resins, epoxy resins, silicone resins, polyimide resins, polystyrene resins, and urethane resins. In the calcination step (S140) described later, these organic resins are carbonized, and the carbide thereof may also function as an adsorbent.
In the granulation step (S130), the granulated material 20 containing the carbide 200, the iron compound 210, and the organic binder 220 is produced.
[2-4 ] calcination step (S140)
In the calcination step (S140), the granulated substance 20 is calcined to produce the adsorbent 10.
The calcination of the granulated substance 20 is performed by heating the granulated substance 20 in a reducing atmosphere. The granulated material 20 contains an organic binder 220. When the organic binder 220 is heated, a reducing gas such as carbon monoxide gas, hydrogen sulfide gas, sulfur dioxide gas, or hydrocarbon gas is generated. Therefore, it is not necessary to additionally introduce a reducing gas, and a reducing atmosphere can be formed using a reducing gas generated from the granulated substance 20. That is, the iron compound 210 can be reduced using the reducing gas generated from the granulated substance 20. Further, since the reducing gas can be generated inside the granulated substance 20, the iron compound 210 inside the granulated substance 20 can be sufficiently reduced. Further, the iron compound 210 is reduced to iron 110 by the reducing gas from the organic binder 220 around the iron compound 210, whereby the iron 110 of the calcined adsorbent 10 has a structure in which it is contained in the porous material of the second carbide 120. Therefore, the amount of adsorption by the adsorbent 10 can be increased.
In addition, from the viewpoint of explosiveness and combustibility, the amount of reducing gas that is difficult to handle is large. Therefore, an inert gas may be contained in the calcination of the granulated substance 20 in order to dilute and discharge the generated reducing gas. As the inert gas, for example, nitrogen gas, argon gas, or the like can be used. When an inert gas is used, for example, nitrogen gas may be flowed to make the concentration of carbon monoxide in the calcining furnace be 1% to 20%.
In addition, the reducing atmosphere may be formed using not only the reducing gas generated from the organic binder 220 but also a reducing gas such as carbon monoxide gas, hydrogen sulfide gas, sulfur dioxide gas, hydrocarbon gas, or a mixed gas thereof. However, even in this case, the amount of reducing gas can be reduced as compared with the conventional method for producing an adsorbent.
The heating temperature for the calcination of the granulated substance 20 is 400 ℃ to 1200 ℃, preferably 400 ℃ to 900 ℃, and more preferably 600 ℃ to 900 ℃. The heating time is 1 minute to 10 hours, preferably 10 minutes to 5 hours. In the method for producing the adsorbent 10 of the present embodiment, since the iron compound 210 can be reduced using the reducing gas generated from the organic binder 220, the heating temperature and the heating time can be reduced as compared with the method for producing a normal adsorbent.
By firing the granulated substance 20, the carbide 200 is changed to the first carbide 100, the iron compound 210 is changed to the iron 110, and the organic binder 220 is changed to the second carbide 120.
Through the above calcination step (S140), the adsorbent 10 containing iron 110 is produced.
As described above, although the first carbide 100 and the second carbide 120 contained in the adsorbent 10 are distinguished based on the difference in the raw material for convenience of explanation, the first carbide 100 and the second carbide 120 are both carbides (different in nature from the carbide 200), and may not be clearly distinguished in the adsorbent 10. In other words, the adsorbent 10 may be said to be carbide containing iron. However, unlike conventional methods for producing iron-containing carbide, the adsorbent 10 has properties different from those of conventional iron-containing carbide, although the mechanism is not clear.
[2-5. evaluation of adsorbent 10 ]
The adsorbent 10 of the present invention produced by the above production method has reduced elution of iron and has excellent adsorption characteristics. The adsorption characteristics of the adsorbent 10 can be evaluated by the following measurement, for example.
[2-5-1. amount of phosphorus adsorbed ]
The adsorbent 10 of the present embodiment can adsorb phosphorus, arsenic, lead, or the like. Among these materials, the adsorbing material 10 is excellent in phosphorus adsorption. The evaluation of the adsorption of phosphorus in the adsorption material 10 can be carried out by a batch sampling test (batch testing). The batch sampling test is a method of calculating the amount of phosphorus adsorbed based on the difference between the concentration of the added phosphorus solution and the concentration of the supernatant after the reaction. The phosphorus solution is prepared by mixing potassium dihydrogen phosphate (KH) 2PO4) Obtained by dissolving in water. In the following examples, the amount of P relative to 1L of water was used as a description of the concentration of the phosphorus solution. That is, the concentration of a phosphorus solution prepared by dissolving 200mg of P in 1L of water is described as 200 mg/L. The adsorption amount of phosphorus in the adsorbent 10 is described as the amount of phosphorus adsorbed per 1g of the adsorbent (the amount of adsorbed phosphorus (mg-P)/1g of the adsorbent).
[2-5-2. specific surface area ]
The specific surface area is a surface area per unit amount and is one of important parameters for porosity. The specific surface area is related to the surface structure of the adsorbent 10, and can be said to be one of the parameters determining the adsorption characteristics. The specific surface area of the adsorbent 10 can be measured, for example, by a gas adsorption method (BET method) based on the BET formula.
In the BET method, the specific surface area of a sample (surface area per 1g of sample) can be calculated from the measurement of the adsorption of gas. Specifically, in the BET method, the specific surface area is determined from the adsorption isotherm. That is, the adsorption amount of the adsorbed gas can be obtained based on the BET formula, and the specific surface area can be obtained by multiplying the area occupied by one molecule of the adsorbed gas on the surface. As the adsorption gas, for example, nitrogen gas, argon gas, krypton gas, carbon monoxide gas, or carbon dioxide gas can be used, and the adsorption amount can be measured by a change in pressure or volume of the gas to be adsorbed. Specific measurement by the BET method is, for example, as a pretreatment, vacuum degassing is performed at a temperature of 120 ℃, nitrogen gas is adsorbed as an adsorption gas, and the specific surface area is calculated from the BET formula.
The specific surface area described in the present specification is typically a specific surface area measured by a BET method using nitrogen as an adsorption gas, but may be a specific surface area measured by a method other than the BET method.
The adsorbent 10 has a specific surface area of 100m2500m above/g2A ratio of 100m or less2More than 400 m/g2A ratio of not more than 150 m/g, preferably2More than 400 m/g2The ratio of the carbon atoms to the carbon atoms is less than g. If the specific surface area of the adsorbent 10 is too small, a sufficient adsorption amount cannot be secured, and thus the adsorption characteristics of the adsorbent 10 are degraded. On the other hand, if the specific surface area of the adsorbent 10 is too large, the density decreases, and therefore the strength of the adsorbent 10 decreases. That is, the adsorbent 10 cannot maintain a certain shape and becomes brittle. Therefore, the specific surface area of the adsorbent 10 is preferably within the above range.
[2-5-3. Total pore volume ]
Both the total pore volume and the specific surface area are important parameters for porosity. The total pore volume is related to the adsorption amount of the adsorbent 10, and can be said to be one of parameters determining the adsorption characteristics of the adsorbent 10. The total pore volume of the adsorbent 10 is the sum of pore volumes calculated from the pore volume distribution indicating the pore diameter and pore volume of the adsorbent 10.
The fine pores can be classified into macropores (d >50nm), mesopores (2 nm. ltoreq. d.ltoreq.50 nm), or micropores (d <2nm), for example, depending on the pore diameter d. Typically, the pore diameters d of the pores may be measured by measuring macropores by mercury intrusion method based on Washburn formula, measuring mesopores by gas adsorption method based on BJH formula (BJH method), and measuring micropores by gas adsorption method based on HK formula (HK method), but the present invention is not limited thereto.
In the mercury intrusion method, the pore diameter d can be calculated from the pressure of mercury injected into a sample based on the Washburn formula. In addition, in the gas adsorption method, the pore diameter d may be calculated from the pressure of the gas injected into the sample based on BJH formula, HK formula, or the like. Therefore, the pore volume distribution showing the pore volume corresponding to the pore diameter d is obtained by measuring the amount of adsorption of the sample by changing the pressure of the injected mercury or gas.
In the present specification, the cumulative pore volume of pores having pore diameters d in the range of 7.5nm to 110000nm is described as the total pore volume.
The total pore volume of the adsorbent 10 is 1000mm3More than g and 3000mm3A ratio of the total weight of the particles to the total weight of the particles is less than or equal to g, preferably 1000mm3More than g and 2700mm3A value of not more than 1000 mm/g, preferably 1000mm 3More than g and 2500mm3The ratio of the carbon atoms to the carbon atoms is less than g. If the total pore volume of the adsorbent 10 is too small, a sufficient adsorption amount cannot be secured, and thus the adsorption characteristics of the adsorbent 10 are degraded. On the other hand, if the total pore volume of the adsorbent 10 is too large, the specific surface area decreases, and therefore the adsorption characteristics of the adsorbent 10 deteriorate. Therefore, the total pore volume of the adsorbent 10 is preferably within the above range.
[2-5-4. iron content ]
The adsorbent 10 has a large increase in the amount of adsorption as compared with conventional activated carbon by including iron 110 in the carbide. Therefore, the content of iron 110 in the adsorbent 10 is related to the adsorption amount, and can be said to be one of the parameters determining the adsorption characteristics of the adsorbent 10. The amount of iron 110 contained in the adsorbent 10 can be measured, for example, by inductively coupled plasma mass spectrometry (ICP-MS).
ICP-MS is a method of ionizing elements contained in a sample using argon plasma as an ion source, and separating and detecting ions based on a mass-to-charge ratio. The element can be specified according to the mass-to-charge ratio of the detected ion, and the amount of the element can be measured by counting the detected ion.
The content of iron 110 in the adsorbent 10 is a ratio of the amount of iron 110 to the amount of the adsorbent 10. The content of iron 110 in the adsorbent 10 can be calculated from the amount of iron 110 measured by ICP-MS and the amount of the adsorbent 10 used for the measurement.
The content of the iron 110 in the adsorbent 10 is 5% to 35%, preferably 5% to 30%, and more preferably 5% to 25%. If the iron content of the adsorbent 10 is too small, the iron effect cannot be exhibited, and thus the adsorption characteristics of the adsorbent 10 are degraded. On the other hand, if the iron content of the adsorbent 10 is too high, iron is eluted when adsorbing phosphorus. Therefore, the iron content of the adsorbent 10 is preferably within the above range.
[2-5-5. organic carbon content ]
In the above-described method for producing the adsorbent 10, the organic binder 220 is kneaded to stably produce the granulated substance 20 in a granular form. The iron compound 210 can be sufficiently reduced to iron 110 by the action of the reducing gas generated from the organic binder 220 of the granulated substance 20. Therefore, in the production of the adsorbent 10, the organic binder 220 can be said to be a very important material. Since the organic binder 220 is changed into the second carbide 120 through the firing process (S140), it is difficult to directly quantify the organic binder 220 by the measurement of the adsorbent 10. However, the present inventors have found that the organic carbon content of the carbide of the adsorbent 10 is related to the adsorption characteristics of the adsorbent 10. The mechanism of this correlation is not necessarily clear, but it is presumed that the organic carbon contained in the carbide of the adsorbent 10 is due to the second carbide 120. Therefore, by measuring the content of the organic carbon contained in the carbide of the adsorbent 10, the content of the second carbide 120 contained in the carbide of the adsorbent 10 can be determined, and the adsorbent 10 can be specified to be manufactured using the organic binder 220. In this regard, the content of organic carbon contained in the carbide of the adsorbent 10 can be said to be one of the parameters determining the adsorption characteristics of the adsorbent 10.
The content of organic carbon contained in the carbide of the adsorbing material 10 can be calculated by subtracting the content of inorganic carbon from the total carbon content. The total carbon content may be calculated, for example, based on the amount of carbon dioxide produced by burning the sample. The content of inorganic carbon can be calculated based on the amount of carbon dioxide liberated from a carbonate or the like by heating a sample while making it acidic, for example. The combustion temperature at the time of measuring the total carbon content is preferably higher than the calcination temperature in the calcination step (S140). For example, if the calcination temperature in the calcination step (S140) is 850 ℃, the combustion temperature when measuring the total carbon content may be 900 ℃. The heating temperature for measuring the inorganic carbon content is preferably lower than the calcination temperature in the calcination step (S140). The heating temperature for determining the inorganic carbon content is, for example, 200 ℃. In addition, the organic carbon content may be calculated by measuring the total carbon content and the inorganic carbon content using a total organic carbon analyzer.
The organic carbon content in the carbide of the adsorbent 10 is a ratio of the amount of organic carbon to the amount of carbide of the adsorbent 10. The organic carbon content in the carbide of the adsorbent 10 can be calculated from the calculated organic carbon content and the measured total carbon content.
The organic carbon content in the carbide of the adsorbent 10 is 30% to 85%, preferably 30% to 75%, and more preferably 35% to 70%.
As described above, the adsorbent 10 according to the embodiment of the present invention does not use any special production equipment, and therefore, the production cost can be reduced. The adsorbent 10 has different parameters than conventional adsorbents, and has excellent adsorption characteristics. The adsorbent 10 having the above parameters, for example, the content of organic carbon in carbide is 30% to 85%, and the specific surface area is 100m2500m above/g2Less than g, total pore volume of 1000mm3More than g and 3000mm3The adsorbent 10 of/g or less has particularly excellent adsorption characteristics. Therefore, specific parameters and adsorption characteristics of the adsorption member 10 will be described with reference to examples.
[ examples ]
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.
< example one >
300g of amorphous charcoal as a carbide and 83g of iron oxide were mixed for 3 minutes to obtain a mixture. The moisture content of charcoal was 7.5%, and the solid content of charcoal was 300 × 92.5% ═ 277.5 g. Thus, the ratio of the amount of solid components of charcoal to the amount of iron oxide was 277.5: and 83 is 100: 30.
Next, the mixture was charged into a mixer (manufactured by Dalton CORPORATION, model: KDRJ-10), 500g of molasses was added thereto at room temperature over 2 minutes, and the mixture was mixed for 30 minutes to obtain a paste. The water content of the waste molasses was 30%, and the solid content of the waste molasses was 500X 70.0% -350.0 g. The content ratio of the solid component amount of the charcoal to the solid component amount of the waste molasses was 277.5: 100 for 350: 126.1.
next, the paste was charged into a granulator (model F-5, manufactured by Darlton, K.K.) and granulated at a rotation speed of 112rpm to obtain granules having a diameter of 6mm and a height of 9 mm.
Next, 50g of the obtained granules were calcined at 750 ℃ for 3 hours in a nitrogen atmosphere using a two-in-one three-zone tubular furnace unit (manufactured by Asahi chemical and chemical industries, ltd.) equipped with a quartz tube, to obtain 25g of the adsorbent a.
The adsorption amount of phosphorus on the adsorbent a was evaluated by a batch method. 0.1g of the adsorbent A was added to 200mg/L of 50ml of a phosphorus solution, and horizontally shaken at 23 ℃ and 100rpm until an equilibrium concentration was reached, followed by filtration. The phosphorus adsorption amount of the adsorbent A was 27.2(mg-P/g) as calculated by analyzing the phosphorus concentration of the filtrate by molybdenum blue spectrophotometry. Further, after the evaluation of the amount of phosphorus adsorbed, no disintegration of the adsorbent a was observed, and it was found that the adsorbent a had high strength in water. Further, the elution amount of iron was 9.4ppm, and it was found that the elution of iron from the adsorbent A was decreased.
< example two >
24g of the adsorbent B was obtained under the same conditions as in example one, except that the calcination temperature was set to 800 ℃.
The amount of phosphorus adsorbed by the adsorbent B was evaluated under the same conditions as in example one. The phosphorus adsorption amount on the adsorbent B was 37.9 (mg-P/g). Further, after the evaluation of the amount of phosphorus adsorbed, no disintegration of the adsorbent B was observed, and it was found that the adsorbent B had high strength in water. Further, the amount of eluted iron was 10.4ppm, and it was found that the elution of iron from the adsorbent B was reduced.
< example three >
22g of an adsorbent C was obtained under the same conditions as in example one, except that the calcination temperature was 850 ℃.
The amount of phosphorus adsorbed by the adsorbent C was evaluated under the same conditions as in example one. The phosphorus adsorption amount of the adsorbent C was 39.2 (mg-P/g). Further, after the evaluation of the amount of phosphorus adsorbed, no disintegration of the adsorbent C was observed, and it was found that the adsorbent C had high strength in water. Further, the elution amount of iron was 9.8ppm, and it was found that the elution of iron from the adsorbent C was decreased.
< comparative example >
In order to confirm the effects of the adsorbent 10 of the present embodiment, the same evaluations as in the first to third examples were performed using commercially available activated carbon as an example of a conventional adsorbent. Specifically, the amount of phosphorus adsorbed by activated carbon was evaluated by the batch method. 0.5g of activated carbon (Egret WH2x, granulated by Osaka gas chemical Co., Ltd.) and 250ml of a 200mg/L phosphorus solution were used. The phosphorus adsorption amount of the activated carbon was 3.5 (mg-P/g).
Based on the above, it is understood that the adsorbents a to C obtained in examples one to three are significantly improved in the phosphorus adsorption amount of the adsorbent 10 of the present embodiment, as compared with the activated carbon of the comparative example.
In addition, in order to compare the differences in properties between the adsorbents a to C obtained in example one and example three and the activated carbon of the comparative example, the specific surface areas, total pore volumes, iron contents, and organic carbon contents of the adsorbents a to C and the activated carbon were evaluated.
The specific surface area was measured using a fully automatic specific surface area measuring apparatus (model: HM model-1201) manufactured by Mountech (mount co., Ltd.).
The pore size distribution was measured using a fully automatic pore size distribution measuring apparatus (model: PoreMaster 33P) manufactured by Quantachrome (Quantachrome). The total pore diameter volume is obtained by integrating pore diameter volumes in the range of pore diameters of 7.5nm or more and 110000nm or less in the pore diameter distribution to be measured.
For the measurement of the iron content, the adsorbent was heated at 100 ℃ for 15 minutes in a 10% hydrochloric acid solution at 100 ℃ and the iron content of the adsorbent was measured by ICP-MS. The iron content in the adsorbent was calculated from the amount of the adsorbent used in the measurement and the measured iron content.
The total organic carbon analyzer manufactured by shimadzu corporation was used for the measurement of the organic carbon content. Further, the carbide content of the organic carbon with respect to the adsorbent was calculated based on the measured organic carbon content and the total carbon content.
Table 1 shows the evaluation results of the adsorbents a to C and activated carbon.
[ TABLE 1 ]
As is clear from table 1, the adsorbent materials a to C have smaller specific surface areas and larger total pore volumes than the activated carbon. Further, it is found that the content of organic carbon in the carbide of the adsorbents a to C is smaller than that of activated carbon. It is presumed that the adsorbents a to C have such properties, and therefore, the phosphorus adsorption amount thereof is significantly increased.
Claims (12)
1. An adsorbent material comprising:
a porous carbide; and the number of the first and second groups,
the amount of iron,
wherein the content of organic carbon in the carbide is 30% or more and 85% or less.
2. An adsorbent material comprising:
a porous carbide; and the number of the first and second groups,
the amount of iron,
wherein the specific surface area of the adsorbent is 100m2500m above/g2The ratio of the carbon atoms to the carbon atoms is less than g.
3. An adsorbent material comprising:
a porous carbide; and the number of the first and second groups,
the amount of iron,
wherein the adsorbent has a total pore volume of 1000mm 3More than g and 3000mm3The ratio of the carbon atoms to the carbon atoms is less than g.
4. The adsorption material of any one of claims 1 to 3,
the iron content is 5% to 35%.
5. The adsorbent material of claim 1,
the content of the organic carbon in the carbide is 50% or more and 85% or less.
6. The adsorbent material of claim 1,
at least a part of the organic carbon is produced by calcining at least one selected from molasses, waste molasses, starch, dextrin, corn starch, rice bran, polyvinyl alcohol, pulp waste liquor, lignosulfonate, carboxymethyl cellulose, hydroxypropyl methyl cellulose, sodium alginate, phenolic resin, and tar pitch.
7. The adsorbent material according to claim 2 or claim 3,
the content of organic carbon in the carbide is 30% to 85%.
8. The adsorbent material according to claim 7,
at least a part of the organic carbon is produced by calcining at least one selected from molasses, waste molasses, starch, dextrin, corn starch, rice bran, polyvinyl alcohol, pulp waste liquor, lignosulfonate, carboxymethyl cellulose, hydroxypropyl methyl cellulose, sodium alginate, phenolic resin, and tar pitch.
9. The adsorbent material according to claim 2 or claim 3,
the content of organic carbon in the carbide is 50% or more and 85% or less.
10. The adsorbent material according to claim 9,
at least a part of the organic carbon is produced by calcining at least one selected from molasses, waste molasses, starch, dextrin, corn starch, rice bran, polyvinyl alcohol, pulp waste liquor, lignosulfonate, carboxymethyl cellulose, hydroxypropyl methyl cellulose, sodium alginate, phenolic resin, and tar pitch.
11. The adsorption material of any one of claims 1 to 3,
the shape is substantially cylindrical.
12. The adsorption material of any one of claims 1 to 3,
the adsorption amount of phosphorus is 5mg-P/g or more.
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| US20060157419A1 (en) * | 2005-01-14 | 2006-07-20 | Clemson University | Activated carbon exhibiting enhanced removal of dissolved natural organic matter from water |
| CN101888970A (en) * | 2008-09-29 | 2010-11-17 | 索尼公司 | Porous carbon material composite, method for producing same, adsorbent, cosmetic preparation, purifying agent and photocatalyst composite material |
| CN103801254A (en) * | 2014-02-25 | 2014-05-21 | 合肥工业大学 | Siderite-based nitrogen and phosphorus removal material and application method thereof |
| CN105688871A (en) * | 2016-04-28 | 2016-06-22 | 江苏省农业科学院 | Preparing method and application of dephosphorization adsorbent carrying nano particle foamed carbon particles |
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| JPH04190847A (en) * | 1990-11-22 | 1992-07-09 | Yasuyoshi Ichiba | Agent for removing tetrachloroethylene in water and preparation thereof |
| JP3840038B2 (en) * | 2000-04-13 | 2006-11-01 | 隆 宮川 | Method for producing adsorptive ceramics |
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| US20060157419A1 (en) * | 2005-01-14 | 2006-07-20 | Clemson University | Activated carbon exhibiting enhanced removal of dissolved natural organic matter from water |
| CN101888970A (en) * | 2008-09-29 | 2010-11-17 | 索尼公司 | Porous carbon material composite, method for producing same, adsorbent, cosmetic preparation, purifying agent and photocatalyst composite material |
| CN103801254A (en) * | 2014-02-25 | 2014-05-21 | 合肥工业大学 | Siderite-based nitrogen and phosphorus removal material and application method thereof |
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