WO2017061117A1 - Dispersion d'adsorbant et procédé d'adsorption - Google Patents

Dispersion d'adsorbant et procédé d'adsorption Download PDF

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WO2017061117A1
WO2017061117A1 PCT/JP2016/004497 JP2016004497W WO2017061117A1 WO 2017061117 A1 WO2017061117 A1 WO 2017061117A1 JP 2016004497 W JP2016004497 W JP 2016004497W WO 2017061117 A1 WO2017061117 A1 WO 2017061117A1
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Prior art keywords
dispersion
anion
adsorbent
iron oxyhydroxide
anion adsorbent
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PCT/JP2016/004497
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English (en)
Japanese (ja)
Inventor
載泰 廣川
剛 野一色
木村　信夫
正登 天池
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高橋金属株式会社
日本曹達株式会社
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Priority to JP2017544199A priority Critical patent/JP6731934B2/ja
Publication of WO2017061117A1 publication Critical patent/WO2017061117A1/fr

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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
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption

Definitions

  • the present invention relates to a dispersion of an adsorbent mainly composed of iron oxyhydroxide.
  • Iron oxyhydroxide includes ⁇ -type, ⁇ -type, ⁇ -type, and amorphous type depending on the crystal structure.
  • iron oxyhydroxide has a wide range of uses such as pigments, magnetic materials, and catalysts, and is required to be a stable dispersion for some uses.
  • Patent Document 4 describes an aqueous suspension containing “iron oxyhydroxide having a particle size of 500 nm or less”, which specifically includes ⁇ -oxyhydroxide having a width represented by the above particle size.
  • Patent Document 5 iron (II) ions are supported on a clay mineral, and iron oxyhydroxide supported by hydrolysis and oxidation is obtained. It is described that it is used as a photocatalyst.
  • Patent Document 6 describes a method for producing a metal hydroxide sol produced in the presence of a compound having a buffering action. Specifically, ⁇ -containing an average particle diameter of about 8 nm and containing a small amount of an aluminum compound. An iron oxyhydroxide sol is described.
  • Patent Document 7 describes an iron oxyhydroxide sol stabilized with hydroxycarboxylic acid and having a median diameter of around 10 nm.
  • Patent Document 8 also describes an iron hydroxide sol produced in the presence of citric acid. These production requires auxiliary components other than iron oxyhydroxide and a solvent, and the process is complicated, and it is avoided that metal hydroxides or carboxylic acids other than iron, which are components derived from the auxiliary components, remain. I can't. In addition, it is stable near neutrality, but is not necessarily stable when acidic. Moreover, there is no description that these can be used as adsorbents.
  • the present inventor has found that a specific dispersion can be easily produced from a specific iron oxyhydroxide without using an auxiliary component, in particular, a stable nano-dispersion. Moreover, as a result of investigating the adsorption behavior using these, it was found that the adsorption rate was remarkably high, and the physical properties different from those of the raw materials were shown. Therefore, it was considered that this was not simply due to the large surface area.
  • the present invention has been completed based on the above findings.
  • the present invention relates to the following inventions.
  • the anion adsorbent dispersion according to (1) having an isoelectric point of pH 6.0 to 8.0.
  • Anion adsorbent dispersion containing 1 g of adsorbent is introduced into 150 mL of an aqueous solution of potassium dihydrogen phosphate having a phosphorous equivalent concentration of 400 mg / L adjusted to pH 3.5 with hydrochloric acid, and stirred at room temperature.
  • the anion adsorbent dispersion liquid according to any one of (1) to (6), wherein, in a batch type adsorption test to be performed, an adsorption amount converted to phosphorus per 1 g of adsorbent after 3 minutes is 22 mg or more.
  • Anion adsorbent dispersion containing 1 g of adsorbent is put into 150 mL of an aqueous solution of potassium dihydrogen phosphate having a phosphorus conversion concentration of 400 mg / L adjusted to pH 3.5 with hydrochloric acid, and stirred at room temperature.
  • the pH of the aqueous phase after 1 hour rises by 0.5 or more with respect to the higher value of 3.5 or the pH of the anion adsorbent dispersion charged.
  • the anion adsorbent dispersion according to any one of (1) to (7).
  • a method of removing and / or recovering anions comprising the step of aggregating and / or precipitating without adding an aggregating agent by adsorbing ions.
  • the iron oxyhydroxide-containing dispersion of the present invention By using the iron oxyhydroxide-containing dispersion of the present invention, a dispersion can be easily produced without using an auxiliary component, and a particularly stable nano-dispersion can be produced.
  • the iron oxyhydroxide-containing dispersion of the present invention has an extremely fast anion adsorption rate.
  • FIG. 4 is a diagram showing a TEM image of iron oxyhydroxide crystals obtained in Reference Example 1.
  • FIG. 6 is a graph showing the particle size distribution of the nano-dispersed liquid obtained in Example 2.
  • FIG. 3 is a diagram showing the zeta potential of the nano-dispersed liquid obtained in Example 2.
  • 4 is a diagram showing a TEM image of nanodispersed particles obtained in Example 2.
  • FIG. It is a figure which shows the FFT analysis result of the nano dispersion particle obtained in Example 2.
  • FIG. It is a figure which shows aggregation and sedimentation of the nano dispersion particle accompanying phosphoric acid adsorption. It is a figure which shows the change of the particle size (distribution and d50) before and behind phosphoric acid adsorption.
  • the anion adsorbent of the present invention is a dispersion liquid in which particles having an average particle diameter d50 of 2 ⁇ m or less and containing iron oxyhydroxide as a main component are dispersed in a solvent.
  • Iron oxyhydroxide is excellent in adsorptivity to anions.
  • Iron oxyhydroxide includes ⁇ -type, ⁇ -type, ⁇ -type, amorphous type, and the like depending on the crystal structure.
  • ⁇ -iron oxyhydroxide is particularly excellent in terms of adsorption performance, and adsorbents such as phosphate ions, phosphite ions, hypophosphite ions, sulfate ions, nitrate ions, fluoride ions, etc.
  • adsorbents such as phosphate ions, phosphite ions, hypophosphite ions, sulfate ions, nitrate ions, fluoride ions, etc.
  • it is also suitable as a raw material for the dispersion of the present invention in that a dispersion can be easily formed.
  • ⁇ -iron oxyhydroxide generally has a hydroxyl group partially substituted with chlorine ions. When in contact with water during manufacturing or use, the chlorine ions are removed, leaving small holes. These vacancies are considered to be involved in the adsorption of anions such as fluorine, and the efficient anion adsorption in the present invention is also considered to be a feature derived from these vacancies.
  • the iron oxyhydroxide in the present invention is preferably ⁇ -iron oxyhydroxide. Further, the content of chlorine ions in ⁇ -iron oxyhydroxide is preferably 0.5% by mass or more, and more preferably 3% by mass or more.
  • the average particle size of the dispersoid particles in the anion adsorbent dispersion of the present invention is preferably 0.2 ⁇ m or less.
  • the anion adsorbent dispersion liquid of the present invention is further preferably a nano dispersion liquid.
  • the nano-dispersion is a dispersion in which so-called nanoparticles having a particle size of 1 ⁇ m or less are dispersed in a liquid phase, and the particles do not settle by standing or normal centrifugation.
  • the average particle size of the nanoparticles contained in the nanodispersion of the present invention is preferably 0.02 to 0.2 ⁇ m, more preferably 0.05 to 0.15 ⁇ m.
  • the nano-dispersed liquid is excellent in that the adsorption efficiency and the adsorption speed are particularly high.
  • the anion adsorbent dispersion of the present invention preferably contains no components other than substances derived from at least one of an iron compound and a base that are essential as raw materials, a pH adjuster, and a solvent. Moreover, it is preferable not to contain an organic acid and its salt, an inorganic weak acid and its salt, a metal oxide and a metal hydroxide (except iron oxide, iron hydroxide, and iron oxyhydroxide), and a dispersing agent. Conventionally, iron oxyhydroxide dispersions usually contain these components as auxiliary components for stabilizing the dispersion, but the present invention requires the use of these auxiliary components in the production process. Absent.
  • the solid content in the anion adsorbent dispersion of the present invention (referred to as a dispersoid and a solute that is a solid at room temperature) has a content of iron compound containing the main component ⁇ -iron oxyhydroxide. It is 99 mass% or more, and it is preferable that the content rate of substances other than an iron compound is 1 mass% or less.
  • the iron oxyhydroxide content is more preferably 99% by mass, and most preferably substantially 100% by mass.
  • the solid concentration in the dispersion is preferably 5% by mass or more.
  • the iron oxyhydroxide used in the present invention preferably has a BET specific surface area of 200 m 2 / g or more, more preferably 250 m 2 / g or more, and more preferably 280 m 2 / g or more.
  • the pore volume area distribution (dV / dR) calculated by the BJH method is preferably 100 to 300 mm 3 / g / nm.
  • the adsorbent dispersion of the present invention is not excellent as an adsorbent simply because of its large specific surface area and pore volume.
  • the adsorbent dispersion of the present invention there is a method using a dry gel mainly composed of iron oxyhydroxide as a raw material, and the dry gel originally has a relatively high surface area. Even if this is pulverized, the specific surface area and the like do not increase particularly. However, when the average particle diameter is 2 ⁇ m or less and a part of the hydroxyl group of iron oxyhydroxide is substituted with chlorine ions, particularly excellent adsorption characteristics are produced.
  • the liquid phase other than the particles in the anion adsorbent dispersion of the present invention can be used without any problem as long as it is a uniform liquid phase.
  • water, an organic solvent, a mixture of water or an organic solvent, or these Can be used.
  • the solution preferably contains no organic acid and salt thereof, weak inorganic acid and salt thereof, and a dispersant.
  • water or an aqueous solution should be used as the liquid phase. preferable.
  • the anion adsorbent dispersion of the present invention can be used as an adsorbent as it is, or can be processed and used as a material for an adsorbent having a different shape or application.
  • the liquid phase component can be removed from the anion adsorbent dispersion of the present invention to form particles, which can be used in the gas phase, but it is preferable to use the dispersion in the form of a dispersion. . Since the anion adsorbent dispersion of the present invention or an adsorbent obtained by processing this dispersion quickly reaches adsorption equilibrium, it can adsorb very efficiently.
  • the particle shape is preferably granular.
  • granular means that it is not needle-shaped or plate-shaped, and more specifically, the ratio of the major axis / minor axis of the crystal is 3 or less.
  • the anion adsorbent dispersion of the present invention preferably has an average crystallite size of 3 nm or less, more preferably 1 to 2 nm.
  • the anion adsorbent dispersion of the present invention is characterized in that the primary particles are composed of a large number of crystallites. Specifically, the ratio of the average particle diameter to the average crystallite diameter is preferably 5 or more, and more preferably 10 to 100. It has been clarified by the present inventors that the smaller the average crystallite size, the higher the phosphate adsorption rate when used as a phosphate adsorbent in water.
  • D K ⁇ / ⁇ cos ⁇
  • ⁇ is the half width of the true diffraction peak corrected for the machine width caused by the apparatus
  • K is the Scherrer constant
  • ⁇ is the wavelength of the X-ray.
  • the anion adsorbent dispersion of the present invention can be obtained by wet-grinding solid ⁇ -iron oxyhydroxide as described later.
  • the average crystallite size of the obtained nanoparticles is about 1 to 2 nm. Since the minimum particle size of the nanoparticles is about 10 nm, which is larger than the original average crystallite size, the crystallite size is not simply destroyed as the particle size decreases, but as a physical effect of the grinding process. It is considered that the decrease is occurring.
  • the anion adsorbent dispersion of the present invention is highly stable on the acidic side from the isoelectric point.
  • This isoelectric point is preferably from pH 5.5 to 8.0, more preferably from pH 6.0 to 8.0, and even more preferably from pH 6.0 to 7.5. In the case of a nano-dispersion, the stability is high at pH 1.5 to 4.0, particularly pH 2.0 to 3.5.
  • the anion adsorbent dispersion liquid of the present invention is stable when the solid content concentration in the dispersion liquid is 5% by mass or more. The solid content concentration is particularly preferably 5 to 10% by mass.
  • the anion adsorbent dispersion of the present invention preferably has a pH of 2.0 to 5.5, more preferably a pH of 2.5 to 5.5, and further preferably a pH of 3.0 to 4.5. preferable.
  • the anion adsorbent dispersion of the present invention has a relatively low viscosity under the above conditions. Specifically, the viscosity is 5 to 20 mPa ⁇ s, more preferably 10 to 15 mPa ⁇ s.
  • the above-described stability factors exhibited by the anion adsorbent dispersion of the present invention are not necessarily clear, but are presumed to be related to the above-mentioned average crystallite diameter or the structural factors described below. .
  • the anion adsorbent dispersion liquid of the present invention is characterized by a high adsorption rate.
  • This adsorption rate can be measured by the following batch adsorption test.
  • a 150 mL aqueous solution of potassium dihydrogen phosphate having a phosphorus conversion concentration of 400 mg / L adjusted to a constant pH with hydrochloric acid is prepared.
  • the anion adsorbent dispersion of the present invention corresponding to 1 g of adsorbent is charged and stirred at room temperature. After a certain period of time, the aqueous solution is sampled and the phosphate ion concentration is measured to determine the amount of adsorption.
  • the liquid phase may be recovered by filtration or, in the case of a nano-dispersion, by ultrafiltration, or the dispersion of the present invention is aggregated or precipitated when phosphate ions are adsorbed as described later. Therefore, if necessary, the supernatant may be collected by centrifugation.
  • the anion adsorbent dispersion of the present invention has a phosphorus equivalent adsorption amount of 22 mg or more, preferably 30 mg or more after 3 minutes.
  • the anion adsorbent dispersion of the present invention is characterized in that the pH rises remarkably in the process of using it as an anion adsorbent in water. This is specifically shown by the following method.
  • a 150 mL aqueous solution of potassium dihydrogen phosphate having a phosphorus conversion concentration of 400 mg / L adjusted to a constant pH with hydrochloric acid is prepared.
  • the anion adsorbent dispersion of the present invention corresponding to 1 g of adsorbent is charged and stirred at room temperature. The aqueous phase is sampled after a certain time and the pH is measured.
  • the liquid phase may be recovered by filtration or, in the case of a nano-dispersion, by ultrafiltration, or the dispersion of the present invention is aggregated or precipitated when phosphate ions are adsorbed as described later. Therefore, if necessary, the supernatant may be collected by centrifugation.
  • the anion adsorbent dispersion of the present invention is 3.5 or higher relative to the pH of the charged anion adsorbent dispersion.
  • the pH of the aqueous solution after 1 hour rises by 0.5 or more.
  • ⁇ -iron oxyhydroxide which can be used as a material for the anion adsorbent dispersion of the present invention as described later, is used as an adsorbent in the same manner as long as the particle diameter is not very small. Also cause little change in the pH of the aqueous solution.
  • the adsorbed anion is exchanged with a hydroxyl group, and the anion is directly bonded to the adsorbent, and the hydroxyl group is a hydroxide ion.
  • the pH of the aqueous solution rises.
  • the anion adsorbent dispersion liquid of the present invention not only simply adsorbs anions, but then the anions bind to the adsorbent and do not easily dissociate. Both are considered to exhibit a very high remarkable adsorption effect.
  • the production method of the adsorbent particles of the present invention is not necessarily limited, but a production method including a step of wet-grinding a solid mainly composed of ⁇ -iron oxyhydroxide is particularly preferable.
  • the solid containing ⁇ -iron oxyhydroxide as a main component is preferably a dry gel obtained by a method including a step of reacting an iron compound-containing solution with a base to form a precipitate at pH 9 or lower.
  • the iron compound is preferably an iron salt, particularly a trivalent iron salt. Specific examples include ferric chloride, ferric sulfate, and ferric nitrate. Among these, ferric chloride is particularly preferable.
  • the base is used to neutralize the acidic iron compound aqueous solution and generate a precipitate containing iron oxyhydroxide. Specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, sodium carbonate, potassium carbonate, calcium carbonate and the like.
  • sodium hydroxide is particularly preferable.
  • the pH during the formation of the precipitate is adjusted to the range of pH 3.3-6. If necessary to adjust this pH, a pH adjusting agent may be used.
  • the pH adjuster substances having a buffering action are excluded because they are difficult to remove, and specific examples include bases as described above and inorganic strong acids such as hydrochloric acid, sulfuric acid, and nitric acid.
  • the precipitate containing iron oxyhydroxide as a main component obtained by the above method can be collected by filtration and dried to form a dry gel.
  • a step of drying the precipitate and a step of drying the precipitate after bringing it into contact with water.
  • the two drying steps are preferably performed at 140 ° C. or less, and more preferably at 100 to 140 ° C.
  • the drying temperature requires a long time at a low temperature and is not suitable for efficient production. Further, there is a tendency that the number of anion adsorption sites tends to decrease at a high temperature, and even higher temperature is not preferable because it changes to iron oxide. Drying can be done in air, vacuum, or in an inert gas.
  • the dry gel obtained by the above method contains ⁇ -iron oxyhydroxide as a main component.
  • the anion adsorbent dispersion liquid of the present invention is particularly suitable for using the dispersoid contained therein as an anion adsorbent in the liquid.
  • the dispersoid contained in the anion adsorbent dispersion liquid of the present invention has the property of aggregating or precipitating without using an aggregating agent when adsorbing anions in the acidic region, and can be easily separated. . In this adsorption step, it is preferable to keep the pH at 5.5 or lower. Therefore, these dispersions can be used as an anion adsorbing material by adding the dispersion to the liquid containing the target anion to aggregate or precipitate the dispersoid, and separating and collecting it.
  • anion adsorbent When the anion is desorbed from the collected anion adsorbent, it can be re-dispersed, and this anion adsorbent can be used repeatedly. Anions can also be recovered by desorption.
  • the above properties are particularly advantageous in the case of a nanodispersion.
  • the dispersoid contained in the nanodispersion cannot be separated by ordinary centrifugation or filtration, and requires a special method such as ultrafiltration.
  • the anion adsorbent dispersion of the present invention can be easily separated and recovered after adsorption.
  • the anion adsorbent dispersion liquid of the present invention is particularly suitable to remove an anion component such as phosphoric acid as an adsorption target and to remove these components from waste water and / or to recover these components.
  • an anion component such as phosphoric acid
  • it can be used as a pharmaceutical for oral administration utilizing adsorptivity, particularly as a pharmaceutical for suppressing the phosphate level in the body, or a material thereof.
  • the X-ray diffraction (XRD) pattern was measured using an X-ray diffractometer Ultima IV (manufactured by Rigaku Corporation). A CuK ⁇ tube was used for the measurement. The average crystallite size was calculated from XRD according to Scherrer's formula.
  • the specific surface area was measured by a gas adsorption method using a specific surface area measuring device MacsorbHM 1210 (manufactured by Mountec).
  • TEM observation and FFT analysis The TEM (transmission electron microscope) observation of the sample was performed using a transmission electron microscope JEM 2010F (manufactured by JEOL, acceleration voltage 200 kV).
  • the laser diffraction / scattering type particle size distribution measuring device LA-920 (manufactured by Horiba Ltd.) is used, the volume-based cumulative 50% particle size (D50), and the volume-based cumulative.
  • the 90% particle size (D90) was measured.
  • the particle size, particle size distribution, cumulative 50% particle size (D50), and cumulative 90% particle size (D90) of the nano-dispersion liquid are measured using a dynamic light scattering particle size distribution analyzer Zeta Sizer Nano S (Spectres). Measured.
  • Zeta potential of dispersed particles The zeta potential was measured using a nanotrack (Nanotrac Wave UZ152, manufactured by Nikkiso Co., Ltd.).
  • NaOH ferric chloride
  • FeCl 3 ferric chloride
  • the particle diameter of the iron oxyhydroxide powder obtained as described above was 0.25 mm to 5 mm. It was confirmed by X-ray diffraction that the crystal structure was ⁇ -iron oxyhydroxide and the average crystallite size was 5 nm.
  • FIG. 1 shows a state observed with a transmission electron microscope (TEM). The crystal shape was granular. The crystallite diameter by TEM observation was 5 to 10 nm, and each crystal was granular, and these were condensed to form particles. The specific surface area was 280 m 2 / g, and the chloride ion content was 5.8 wt%.
  • the above-mentioned iron oxyhydroxide powder was dry-pulverized with a pin mill until the particle diameter was about 300 ⁇ m or less to obtain a powder, which was used below.
  • Comparative Example 1 The pulverized iron oxyhydroxide was classified with a sieve to obtain a powder A having a particle size of 150 to 250 ⁇ m.
  • Example 1 (Production of iron oxyhydroxide dispersion)
  • the pulverized iron oxyhydroxide was mixed with ion-exchanged water so as to have a solid concentration of 10% by mass, and then pulverized with a bead mill (zirconia beads, bead diameter: 1 mm) for 30 minutes to obtain a dispersion B.
  • Dispersion B settled slowly when stored at room temperature, but returned to the dispersion again when stirred.
  • the pH of dispersion B was 2.9, the average particle diameter d50 was 1.30 ⁇ m, d90 was 4.35 ⁇ m, and the isoelectric point was pH 7.0.
  • the crystal structure of the powder obtained by drying Dispersion B at 50 ° C. was ⁇ -iron oxyhydroxide, and the specific surface area was 285 m 2 / g.
  • Example 2 (Production of iron oxyhydroxide nanodispersion) Dispersion B was further pulverized for 60 minutes with a bead mill (zirconia beads, bead diameter 0.1 mm). By this pulverization, the liquid suspended in brown was changed to a black and almost transparent nano-dispersion (nano-dispersion C). When nanodispersion C was spread thinly and dried, a film was obtained, and when thickened and dried, solid particles similar to the iron oxyhydroxide powder of Reference Example 1 were obtained. Moreover, it also has a binder function that adheres firmly when dried on a support, and can be molded into various shapes despite being an inorganic substance. Furthermore, the nano-dispersion C was stable even if it passed for one year at room temperature, but it did not gel but was stable, and when dispersed, the dispersion state was easily recovered.
  • the pH of the obtained nanodispersion C was 3.1.
  • the viscosity was 10.9 mPa ⁇ s.
  • the specific surface area of the nano-dispersed particles was 285 m 2 / g.
  • the particle size distribution of the nanodispersion C is shown in FIG.
  • the average particle diameter d50 was 0.05 ⁇ m, and d90 was 0.19 ⁇ m.
  • the measurement result of the zeta potential is shown in FIG.
  • the isoelectric point was pH 7.1, and at pH 3.1, the particles were positively charged.
  • the nano-dispersion was dried at 50 ° C. to obtain a powder.
  • the dry powder was subjected to X-ray diffraction, TEM observation, and fast Fourier transform (FFT) analysis of the TEM image.
  • the TEM image is shown in FIG. 4, and the FFT analysis result is shown in FIG.
  • the average particle diameter was about 3 nm
  • the crystal shape by TEM observation was granular
  • most of the particles were crystal particles in which crystal fringes were observed. These were identified as ⁇ -iron oxyhydroxide crystals from the lattice spacing determined by FFT analysis.
  • Measurement example 1 Potassium dihydrogen phosphate was dissolved in ion-exchanged water, adjusted to pH 3.5 with hydrochloric acid, and a test solution D having a concentration of 400 mg-P / L (concentration as phosphorus) was prepared. Further, potassium dihydrogen phosphate was dissolved in ion-exchanged water, adjusted to pH 7.0 with sodium hydroxide, and a test solution E having a concentration of 400 mg-P / L (concentration as phosphorus) was prepared. After adding 20 g of dispersion B or C (1 g as a solid content) to 130 mL of test liquid D or E, the mixture was stirred and subjected to an adsorption test.
  • the liquid was collected after a predetermined time, separated from the solid content with a filter syringe, and the phosphorus concentration in the solution was analyzed by ICP (inductively coupled plasma) to calculate the amount of adsorption. At the same time, the pH was measured (Table 1).
  • Measurement example 2 (sedimentation test) To 130 mL of the test liquid D, 20 g of nano-dispersion C (1 g as a solid content) was added and mixed and allowed to stand. As a result, the nano-dispersed particles quickly aggregated and settled. The state (non-adsorbed, standing 15 minutes, 60 minutes and 24 hours later) is shown in FIG. In addition, FIG. 7 shows changes in particle size (non-adsorbed, standing 15 minutes, 30 minutes, 60 minutes, 6 hours, 24 hours).
  • the anion adsorbent dispersion liquid of the present invention has a remarkably high phosphoric acid adsorption rate and a large adsorption amount particularly at pH 3.5. Further, when the initial pH was set to 3.5, a characteristic that was significantly different from the raw material ⁇ -iron oxyhydroxide powder was revealed in that the pH increased to 4 or more in about 1 hour. Furthermore, when the initial pH was 3.5, the particles aggregated and precipitated with the adsorption of phosphoric acid and could be easily recovered.

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Abstract

La présente invention a pour but de fournir une dispersion d'adsorbant-anion qui comporte une nano-dispersion d'oxyhydroxyde de fer qui est stable et qui ne contient aucun constituant dérivé d'un constituant auxiliaire. Cette dispersion d'adsorbant-anion est formée par dispersion, dans un solvant, de particules qui ont un oxyhydroxyde de fer comme constituant principal et un diamètre moyen d50 de particule de 2 µm ou moins. L'oxyhydroxyde de fer est de préférence le β-oxyhydroxyde de fer. De plus, le diamètre moyen d50 des particules qui ont un oxyhydroxyde de fer comme constituant principal est de préférence de 0,2 µm ou moins.
PCT/JP2016/004497 2015-10-09 2016-10-06 Dispersion d'adsorbant et procédé d'adsorption WO2017061117A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018015703A (ja) * 2016-07-27 2018-02-01 清水建設株式会社 陰イオン吸着方法及び陰イオン吸着体
JPWO2017110736A1 (ja) * 2015-12-25 2018-09-13 高橋金属株式会社 吸着材粒子
CN113772906A (zh) * 2021-09-22 2021-12-10 同济大学 利用酸性离子交换树脂预处理强化污泥生物资源化的方法

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JPWO2017110736A1 (ja) * 2015-12-25 2018-09-13 高橋金属株式会社 吸着材粒子
JP2018015703A (ja) * 2016-07-27 2018-02-01 清水建設株式会社 陰イオン吸着方法及び陰イオン吸着体
CN113772906A (zh) * 2021-09-22 2021-12-10 同济大学 利用酸性离子交换树脂预处理强化污泥生物资源化的方法
CN113772906B (zh) * 2021-09-22 2022-09-09 同济大学 利用酸性离子交换树脂预处理强化污泥生物资源化的方法

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