WO2017150426A1 - Calcium oxide powder and adsorbent, and method for producing calcium oxide powder - Google Patents

Calcium oxide powder and adsorbent, and method for producing calcium oxide powder Download PDF

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WO2017150426A1
WO2017150426A1 PCT/JP2017/007396 JP2017007396W WO2017150426A1 WO 2017150426 A1 WO2017150426 A1 WO 2017150426A1 JP 2017007396 W JP2017007396 W JP 2017007396W WO 2017150426 A1 WO2017150426 A1 WO 2017150426A1
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calcium oxide
oxide powder
range
water vapor
particle size
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PCT/JP2017/007396
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French (fr)
Japanese (ja)
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浩二 小久保
加藤　裕三
渡辺　高行
孝之 大渕
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宇部マテリアルズ株式会社
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Application filed by 宇部マテリアルズ株式会社 filed Critical 宇部マテリアルズ株式会社
Priority to JP2018503280A priority Critical patent/JP6759327B2/en
Priority to KR1020187027005A priority patent/KR102596127B1/en
Priority to CN201780012106.5A priority patent/CN108698848B/en
Publication of WO2017150426A1 publication Critical patent/WO2017150426A1/en

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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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • 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
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C01F11/04—Oxides or hydroxides by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the present invention relates to a calcium oxide powder and an adsorbent and a method for producing calcium oxide powder, and more particularly to a calcium oxide powder and an adsorbent suitable for adsorption of moisture and acid gas, and a method for producing calcium oxide powder.
  • quicklime calcium oxide
  • a dehydrating agent a basic furnace material
  • a cement material a cement material
  • a moisture adsorbent ie, a hygroscopic agent
  • an acid gas adsorbent in electronic devices such as organic EL displays and sensors, and vacuum insulation materials, utilizing its high reactivity with water and acid.
  • finely divided adsorbents are required.
  • Patent Document 1 discloses that the BET specific surface area is 60 m 2 / g or more, the total pore volume of pores in the diameter range of 2 to 100 nm is 0.35 ml / g or more, and the particle diameter is 0.00.
  • a calcium oxide powder containing 80% by mass or more of particles of 25 mm or less is disclosed.
  • This document also discloses a method for producing a highly reactive calcium oxide powder by calcining calcium hydroxide powder at a temperature of 315 to 500 ° C. under a pressure of 300 Pa or less.
  • Patent Document 2 the amount of increase in mass when it is allowed to stand for 1 hour in an atmosphere adjusted to a temperature of 23 ° C. and a relative humidity of 45% RH is 0.15 g or more per 1 cm 3.
  • Quicklime is described.
  • the granular quicklime of this literature contains 50 mass% or more of particles having a particle diameter of 0.075 mm or more and does not contain 10 mass% or more of particles having a particle diameter of 1.0 mm or more.
  • granular slaked lime having a loose apparent bulk density in the range of 0.5 to 1.0 g / cm 3 and a BET specific surface area of 10 m 2 / g or more is obtained under a pressure of 300 Pa or less and from 325 to
  • a method for producing granular quicklime that is fired at a temperature of 500 ° C. for 1 hour or more is also described.
  • Patent Document 3 describes a moisture adsorbent that is mainly composed of calcium oxide particles having an aprotic polar solvent layer, and is hydrophobic and has a high adsorption rate. Further, it is described that the BET specific surface area of the water adsorbent described in this document is preferably 1 to 100 m 2 / g, and the average particle diameter is preferably 0.05 to 10 ⁇ m. Furthermore, this document also describes a method for producing a moisture adsorbent in which calcium oxide is pulverized in the presence of an aprotic organic solvent.
  • Japanese Patent No. 5165213 see claims 1 and 6, paragraph 0029
  • Japanese Patent No. 4387870 see claim 1, paragraph 0024
  • International Publication No. 2014/109330 see claim 1, paragraph 0011
  • Patent Documents 1 and 2 since the average particle diameter is relatively large, there is still room for improvement in terms of particle miniaturization.
  • calcium oxide produced by vacuum firing as in these documents tends to have low chemical reactivity with water and acid gas because of low crystallinity.
  • it is necessary to adsorb low density moisture and acid gas so the contribution of chemical reactivity is large, and simply increasing the specific surface area can optimize the adsorption performance.
  • a vacuum firing furnace is required for the production of calcium oxide powder, the cost tends to be high, and there is room for improvement in terms of cost.
  • Patent Document 3 Calcium oxide of Patent Document 3 has excellent adsorption performance, but it can affect the performance of electronic equipment and the degree of vacuum in the vacuum heat insulating material by evaporating the aprotic organic solvent coated on the particle surface. There is sex.
  • An object of the present invention is to provide a calcium oxide powder and an adsorbent which have fine particles and are excellent in moisture and acid gas adsorption, and a method for producing the calcium oxide powder.
  • the inventors of the present invention produced calcium oxide powder by a predetermined production method, so that the particles were minute and excellent in moisture and acid gas adsorption.
  • the inventors have found that calcium oxide powder can be produced, and have completed the present invention.
  • the present invention has an average particle size of 10 ⁇ m or less, a BET specific surface area of 10 to 30 m 2 / g, a basicity of 25 to 100 ⁇ mol / m 2 , and a water vapor pressure of 100 Pa.
  • the calcium oxide powder is characterized in that the water vapor adsorption amount below is 200 ml / g or more.
  • the particle size distribution (D90) is preferably in the range of 1 to 8 ⁇ m.
  • the present invention is an adsorbent characterized by containing the calcium oxide powder described in any of the above.
  • the present invention also includes a firing step in which calcium hydroxide is fired in the air under conditions within a range of 500 to 700 ° C. to generate calcium oxide, and a pulverizing step in which the calcium oxide is pulverized into a powder. It is a manufacturing method of the calcium oxide powder characterized by providing.
  • a calcium oxide powder an adsorbent, and a method for producing calcium oxide powder that have fine particles and are excellent in moisture and acid gas adsorption.
  • the calcium oxide powder of the present invention has an average particle size of 10 ⁇ m or less, a BET specific surface area of 10 to 30 m 2 / g, a basicity of 25 to 100 ⁇ mol / m 2 , and a water vapor pressure of 100 Pa.
  • the amount of water vapor adsorption under the above conditions is 200 ml / g or more.
  • the average particle diameter of the calcium oxide powder is 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the lower limit of the average particle diameter of the calcium oxide powder is not particularly limited, but is usually 10 nm or more. Calcium oxide powder having an average particle diameter of less than 10 nm is difficult to produce, and the particle diameter is too small to be easily handled.
  • the BET specific surface area of the calcium oxide powder is in the range of 10 to 30 m 2 / g, preferably in the range of 12 to 25 m 2 / g, and more preferably in the range of 15 to 20 m 2 / g.
  • the BET specific surface area of the calcium oxide powder is less than 10 m 2 / g, the adsorption rate of moisture and acid gas tends to be slow.
  • the BET specific surface area of the calcium oxide powder exceeds 30 m 2 / g, the adsorption rate of moisture and acid gas is too high and the handling tends to be difficult. Accordingly, when the BET specific surface area of the calcium oxide powder is within the range of 10 to 30 m 2 / g, the adsorption rate of moisture and acid gas is appropriate, and the handleability is good.
  • the basicity of the calcium oxide powder is in the range of 25 to 100 ⁇ mol / m 2 , preferably in the range of 28 to 50 ⁇ mol / m 2 , and more preferably in the range of 30 to 40 ⁇ mol / m 2 .
  • the basicity of the calcium oxide powder is less than 25 ⁇ mol / m 2 , the acid gas adsorption rate tends to be slow.
  • the basicity of the calcium oxide powder exceeds 100 ⁇ mol / m 2 , the acid gas adsorption rate is too high, and the handling tends to be difficult.
  • the acid gas adsorption rate is appropriate and the handleability is good.
  • the basicity mentioned here is defined by the amount of carbon dioxide adsorbed per 1 m 2 / g of the specific surface area of calcium oxide, and means a value measured by the method described in the examples described later or a method according thereto.
  • the water vapor adsorption amount of the calcium oxide powder under a water vapor pressure of 100 Pa is 200 ml / g or more, preferably 230 ml / g or more, more preferably 250 ml / g or more.
  • the upper limit of the water vapor adsorption amount is not particularly limited, but is usually 5000 ml / g or less, 1000 ml / g or less, and 500 ml / g or less.
  • the 90% particle size in the particle size distribution of the calcium oxide powder is not particularly limited, but is usually in the range of 1 to 8 ⁇ m, preferably 2 It is in the range of ⁇ 7 ⁇ m, more preferably in the range of 3 to 6 ⁇ m.
  • D90 of the calcium oxide powder exceeds 8 ⁇ m, the particle size becomes too large, so that it tends to be unsuitable for small electronic devices, heat insulating materials, etc., and the appearance tends to deteriorate when used as a coating or filling material.
  • the D90 of the calcium oxide powder is less than 1 ⁇ m, it is difficult to produce, and the particle size is too small to be easily handled.
  • calcium oxide is in direct contact with the outside air without being coated on the surface, and has a high BET specific surface area and basicity, so that low density (low pressure) moisture and acid gas are particularly effective. Can be absorbed into.
  • the calcium oxide powder of the present invention since the calcium oxide powder of the present invention has a small average particle size and is pulverized, it can cope with downsizing and thinning of electronic devices and heat insulating materials.
  • the calcium oxide powder of the present invention is particularly suitable for use as a hygroscopic agent for a vacuum heat insulating material and an adsorbent for an acidic gas.
  • the vacuum heat insulating material is a heat insulating material in which a core material is stored in a laminated film processed into a bag shape and then the inside of the laminated film is decompressed and sealed. When air or moisture penetrates into the laminate film, the heat insulating property is lowered.However, by blending the calcium oxide powder of the present invention into the laminate film, the gas caused by the calcium oxide powder is prevented while preventing the entry of air and moisture. Since there is no generation
  • the calcium oxide powder of the present invention is suitable as a hygroscopic agent for electronic devices such as organic EL and an adsorbent for acidic gas.
  • the calcium oxide powder of the present invention can be used after being dispersed in a synthetic resin and formed into a sheet, pellet, plate, or film. These molded products can be advantageously used as a desiccant for electronic devices such as organic EL displays.
  • synthetic resin polyolefin resin, polyacrylic resin, polyacrylonitrile resin, polyamide resin, polyester resin, epoxy resin, polycarbonate resin, and fluorine resin can be used.
  • the calcium oxide powder of the present invention can be used by being housed in a moisture-permeable bag or container used in a normal hygroscopic agent. By doing in this way, the slight water
  • the calcium oxide powder may be used alone or in combination with other hygroscopic materials (for example, silica gel or molecular sieve).
  • Calcium oxide of the present invention may be used as it is in powder form or may be used after being formed into an arbitrary shape. Further, it can be used as a paint filled with an appropriate solvent or polymer material of the calcium oxide of the present invention, a tape or a film filled with a polymer material, and the like. For this reason, desiccants for electronic devices that repel moisture such as organic EL and liquid crystals, desiccants for heat insulation layers such as refrigerators and double glass, moisture adsorption layers for barrier films, and packing for sealed containers (chemicals, pharmaceuticals, It can also be suitably used for food deterioration prevention), application to the inner surface of vacuum piping, O-ring use (maintaining high vacuum), and the like.
  • the calcium oxide production method of the present invention is obtained by a calcining step in which calcium hydroxide is calcined in the air under conditions within a range of 500 to 700 ° C. to generate calcium oxide, and the calcining step.
  • the firing step is a step of firing calcium hydroxide as a raw material to generate calcium oxide.
  • the kind and manufacturing method of calcium hydroxide (slaked lime), For example, what added water to calcium oxide and hydrated etc. can be used.
  • the firing step is performed at a high temperature in the range of 500 to 700 ° C. and in the air.
  • the firing temperature is lower than 500 ° C., the crystallinity of the calcium oxide powder obtained due to insufficient firing is lowered, and the adsorptivity of moisture and acid gas tends to be lowered.
  • the firing temperature exceeds 700 ° C., the BET specific surface area becomes small, and the adsorptivity of moisture and acid gas tends to be low.
  • the firing time is not particularly limited, but is usually in the range of 30 minutes to 30 hours.
  • the firing step firing is performed in air, that is, in air and at atmospheric pressure (about 0.1 MPa).
  • air that is, in air and at atmospheric pressure (about 0.1 MPa).
  • generate is high, As a result, the basicity is high and the adsorptivity of acidic gas becomes excellent.
  • baking process in the air baking can be performed at a lower cost than in the case of performing vacuum baking.
  • the crushing step is a step of crushing calcium oxide obtained in the firing step into a powder form. By performing pulverization after firing, a calcium oxide powder having a small particle diameter and a high BET specific surface area can be produced.
  • the pulverization method is not particularly limited, and a pulverizer such as a media mill, a rotating ball mill, a vibration ball mill, a planetary ball mill, a rocking mill, a paint shaker, and an airflow pulverizer can be used.
  • a pulverizer such as a media mill, a rotating ball mill, a vibration ball mill, a planetary ball mill, a rocking mill, a paint shaker, and an airflow pulverizer can be used.
  • an airflow pulverizer is preferable, and a jet mill is particularly preferable because a fine and sharp powder having a particle size distribution can be obtained.
  • a sharp particle size distribution of the calcium oxide powder is preferable because the moisture absorption rate of the calcium oxide powder is stabilized.
  • the pulverization conditions in the jet mill are, for example, in an inert gas atmosphere such as nitrogen or argon, and at a raw material supply rate of 5 kg / h, the pulverization pressure is 0.3 to 1.5 MPa, more preferably 0. It is preferably 3 to 1.0 MPa.
  • the classification step can be performed using a sieve with an appropriate opening.
  • the average particle diameter of calcium oxide is preferably 10 ⁇ m or less, and the particle size distribution is preferably adjusted so that the particle size distribution (D90) is in the range of 1 to 8 ⁇ m.
  • the BET specific surface area was measured by the BET single point method using Monosorb (manufactured by Quantachrome Instruments).
  • the water vapor adsorption amount is determined by measuring the water vapor adsorption isotherm using a highly accurate fully automatic gas adsorption device BELSORP18 (manufactured by Nippon Bell Co., Ltd.) and calculating the water adsorption amount (g / g) per 1 g of calcium oxide at a water vapor pressure of 100 Pa It was measured.
  • the moisture adsorption amount is a value converted into a gas volume in a standard state (0 ° C., 1 atm).
  • Ethanol was used as a dispersion solvent for the sample, and dispersion treatment was performed for 3 minutes with an ultrasonic homogenizer (MODEL US-150T, manufactured by Nippon Seiki Seisakusho Co., Ltd.).
  • the dispersed sample was measured for the average particle size and particle size distribution (D90) using a laser diffraction particle size distribution analyzer (MICROTRAC HRA9320-X100, manufactured by Nikkiso Co., Ltd.).
  • Example 1 Calcium hydroxide fine powder (CH-2N Ube Materials Co., Ltd.) is fired in the atmosphere at 600 ° C. for 10 hours, and supplied in a nitrogen atmosphere using a jet mill (STJ-200 Seisin Enterprise Co., Ltd.) 5 kg / h, The powder was pulverized under the pressure of 0.7 MPa to obtain calcium oxide powder.
  • the obtained calcium oxide powder had a BET specific surface area of 17.0 m 2 / g and a basicity of 45.9 ⁇ mol / m 2 .
  • the water vapor adsorption amount was 265 ml / g at a water vapor pressure of 100 Pa.
  • the average particle size was 1.8 ⁇ m, and D90 was 3.1 ⁇ m. The results are shown in Table 1.
  • Example 2 Calcium hydroxide fine powder (CH-2N Ube Materials Co., Ltd.) is calcined in the atmosphere at 600 ° C. for 10 hours and supplied in a nitrogen atmosphere using a jet mill (STJ-200 Seisin Enterprise Co., Ltd.). h, The powder was pulverized under the pressure of 0.7 MPa to obtain calcium oxide powder.
  • the obtained calcium oxide powder had a BET specific surface area of 16.8 m 2 / g and a basicity of 36.5 ⁇ mol / m 2 .
  • the water vapor adsorption amount was 232 ml / g at a water vapor pressure of 100 Pa.
  • the average particle size was 1.8 ⁇ m, and D90 was 3.2 ⁇ m. The results are shown in Table 1.
  • the calcium oxides of Examples 1 and 2 have a basicity in the range of 25 to 100 ⁇ mol / m 2 , so that they have excellent acid gas adsorptivity and water vapor adsorption amount under the condition of water vapor pressure of 100 Pa.
  • the vacuum fired product as in Comparative Example 1 had a larger BET specific surface area and particle size distribution than Examples 1 and 2, and was inferior in basicity and water vapor adsorption.
  • Comparative Example 3 was found to have a larger particle size than Examples 1 to 3. Furthermore, it was found that the surface treated with N-methylpyrrolidone as in Comparative Example 4 was inferior in the water vapor adsorption amount as compared with Examples 1 to 3.

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  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Drying Of Gases (AREA)

Abstract

Provided is a calcium oxide powder characterized in that the average particle size is 10 μm or less, the BET specific surface area is within the range of 10-30 m2/g, the basicity is within the range of 25-100 μmol/m2, and the amount of water vapor adsorbed under a water vapor pressure of 100 Pa is 200 mL/g or higher. In this case, the grain size distribution (D90) is preferably within the range of 1-8 μm. Furthermore, provided is a method for producing calcium oxide powder, the method being characterized by being provided with a step for firing calcium oxide in air within a range of 500-700°C and a step for pulverizing the calcium oxide after firing. In this case, a step for sorting the calcium oxide after pulverization is also preferably provided.

Description

酸化カルシウム粉末及び吸着剤並びに酸化カルシウム粉末の製造方法Calcium oxide powder, adsorbent and method for producing calcium oxide powder
　本発明は、酸化カルシウム粉末及び吸着剤並びに酸化カルシウム粉末の製造方法に関し、特に、水分や酸性ガスの吸着に適した酸化カルシウム粉末及び吸着剤並びに酸化カルシウム粉末の製造方法に関する。 The present invention relates to a calcium oxide powder and an adsorbent and a method for producing calcium oxide powder, and more particularly to a calcium oxide powder and an adsorbent suitable for adsorption of moisture and acid gas, and a method for producing calcium oxide powder.
　従来、生石灰（酸化カルシウム）は、吸湿剤、脱水剤、塩基性炉材、セメント材料などに利用されている。特に、最近では、水や酸との高い反応性を利用して、有機ＥＬディスプレイやセンサーなどの電子機器や真空断熱材における水分の吸着剤（すなわち、吸湿剤）や酸性ガスの吸着剤として利用することが検討されている。近年では、電子機器・断熱材の小型化や薄膜化に伴い、微粉化した吸着剤が求められている。 Conventionally, quicklime (calcium oxide) is used as a hygroscopic agent, a dehydrating agent, a basic furnace material, a cement material, and the like. In particular, recently, it has been used as a moisture adsorbent (ie, a hygroscopic agent) and an acid gas adsorbent in electronic devices such as organic EL displays and sensors, and vacuum insulation materials, utilizing its high reactivity with water and acid. To be considered. In recent years, with the downsizing and thinning of electronic devices and heat insulating materials, finely divided adsorbents are required.
　例えば、特許文献１には、ＢＥＴ比表面積が６０ｍ２／ｇ以上で、直径２～１００ｎｍの範囲にある細孔の全細孔容積が０．３５ｍｌ／ｇ以上であって、粒子径が０．２５ｍｍ以下の粒子を８０質量％以上含有する酸化カルシウム粉末が開示されている。また、本文献には、水酸化カルシウム粉末を３００Ｐａ以下の圧力下、３１５～５００℃の温度にて焼成することにより、反応性の高い酸化カルシウム粉末を製造する方法も開示されている。 For example, Patent Document 1 discloses that the BET specific surface area is 60 m 2 / g or more, the total pore volume of pores in the diameter range of 2 to 100 nm is 0.35 ml / g or more, and the particle diameter is 0.00. A calcium oxide powder containing 80% by mass or more of particles of 25 mm or less is disclosed. This document also discloses a method for producing a highly reactive calcium oxide powder by calcining calcium hydroxide powder at a temperature of 315 to 500 ° C. under a pressure of 300 Pa or less.
　また、特許文献２には、温度２３℃、相対湿度４５％ＲＨの調整された大気中に１時間静置したときの質量増加量が、１ｃｍ３あたりに換算して０．１５ｇ以上である粒状生石灰が記載されている。また、本文献の粒状生石灰は、粒子径が０．０７５ｍｍ以上の粒子を５０質量％以上含み、粒子径が１．０ｍｍ以上の粒子を１０質量％以上含まないことも記載されている。さらに、本文献には、ゆるみ見掛けかさ密度が０．５～１．０ｇ／ｃｍ３の範囲にあり、かつＢＥＴ比表面積が１０ｍ２／ｇ以上の粒状消石灰を、３００Ｐａ以下の圧力下、３２５～５００℃の温度にて１時間以上焼成する粒状生石灰の製造方法も記載されている。 Further, in Patent Document 2, the amount of increase in mass when it is allowed to stand for 1 hour in an atmosphere adjusted to a temperature of 23 ° C. and a relative humidity of 45% RH is 0.15 g or more per 1 cm 3. Quicklime is described. Moreover, it is described that the granular quicklime of this literature contains 50 mass% or more of particles having a particle diameter of 0.075 mm or more and does not contain 10 mass% or more of particles having a particle diameter of 1.0 mm or more. Further, in this document, granular slaked lime having a loose apparent bulk density in the range of 0.5 to 1.0 g / cm 3 and a BET specific surface area of 10 m 2 / g or more is obtained under a pressure of 300 Pa or less and from 325 to A method for producing granular quicklime that is fired at a temperature of 500 ° C. for 1 hour or more is also described.
　さらに、特許文献３には、非プロトン性極性溶媒層を有する酸化カルシウム粒子を主成分とし、疎水性かつ高い吸着速度を兼ね備えた水分吸着剤が記載されている。また、本文献に記載された水分吸着剤のＢＥＴ比表面積は１～１００ｍ２／ｇが好ましいこと、平均粒子径は０．０５～１０μｍが好ましいことが記載されている。さらに、本文献には、酸化カルシウムを非プロトン性有機溶媒存在下で微粉化する水分吸着剤の製造方法も記載されている。 Furthermore, Patent Document 3 describes a moisture adsorbent that is mainly composed of calcium oxide particles having an aprotic polar solvent layer, and is hydrophobic and has a high adsorption rate. Further, it is described that the BET specific surface area of the water adsorbent described in this document is preferably 1 to 100 m 2 / g, and the average particle diameter is preferably 0.05 to 10 μm. Furthermore, this document also describes a method for producing a moisture adsorbent in which calcium oxide is pulverized in the presence of an aprotic organic solvent.
特許第５１６５２１３号公報（請求項１，６、段落００２９参照）Japanese Patent No. 5165213 (see claims 1 and 6, paragraph 0029) 特許第４３８７８７０号公報（請求項１、段落００２４参照）Japanese Patent No. 4387870 (see claim 1, paragraph 0024) 国際公開第２０１４／１０９３３０号（請求項１、段落００１１参照）International Publication No. 2014/109330 (see claim 1, paragraph 0011)
　特許文献１，２では、平均粒子径が比較的大きいため、粒子の微小化の点においてまだ改善の余地があった。また、これらの文献のように真空焼成で製造した酸化カルシウムは、結晶性が低いため、水や酸性ガスとの化学反応性が低くなりがちである。
特に、電子機器用や真空断熱材では低密度の水分や酸性ガスを吸着する必要があるため、化学反応性の寄与が大きく、単に比表面積を大きくしただけでは、吸着性能を最適化することが困難である。また、酸化カルシウム粉末の製造に真空焼成炉が必要であるため高コストになりがちであり、コスト面で改善の余地があった。 In Patent Documents 1 and 2, since the average particle diameter is relatively large, there is still room for improvement in terms of particle miniaturization. In addition, calcium oxide produced by vacuum firing as in these documents tends to have low chemical reactivity with water and acid gas because of low crystallinity.
Especially for electronic equipment and vacuum insulation materials, it is necessary to adsorb low density moisture and acid gas, so the contribution of chemical reactivity is large, and simply increasing the specific surface area can optimize the adsorption performance. Have difficulty. Moreover, since a vacuum firing furnace is required for the production of calcium oxide powder, the cost tends to be high, and there is room for improvement in terms of cost.
　特許文献３の酸化カルシウムは、吸着性能にすぐれているが、粒子表面に被膜された非プロトン性有機溶媒が気化することにより、電子機器の性能や真空断熱材中の真空度に影響を与える可能性がある。 Calcium oxide of Patent Document 3 has excellent adsorption performance, but it can affect the performance of electronic equipment and the degree of vacuum in the vacuum heat insulating material by evaporating the aprotic organic solvent coated on the particle surface. There is sex.
　本発明の目的は、粒子が微小であり、水分及び酸性ガスの吸着性に優れた酸化カルシウム粉末及び吸着剤並びに酸化カルシウム粉末の製造方法を提供することにある。 An object of the present invention is to provide a calcium oxide powder and an adsorbent which have fine particles and are excellent in moisture and acid gas adsorption, and a method for producing the calcium oxide powder.
　本発明者らは、以上の目的を達成するために、鋭意検討した結果、所定の製造方法で酸化カルシウム粉末を製造することで、粒子が微小であり、水分及び酸性ガスの吸着性に優れた酸化カルシウム粉末を製造できることを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the inventors of the present invention produced calcium oxide powder by a predetermined production method, so that the particles were minute and excellent in moisture and acid gas adsorption. The inventors have found that calcium oxide powder can be produced, and have completed the present invention.
　すなわち、本発明は、平均粒子径が１０μｍ以下であり、ＢＥＴ比表面積１０～３０ｍ２／ｇの範囲内であり、塩基度が２５～１００μｍｏｌ／ｍ２の範囲内であり、水蒸気圧１００Ｐａの条件下における水蒸気吸着量が２００ｍｌ／ｇ以上であることを特徴とする酸化カルシウム粉末である。 That is, the present invention has an average particle size of 10 μm or less, a BET specific surface area of 10 to 30 m 2 / g, a basicity of 25 to 100 μmol / m 2 , and a water vapor pressure of 100 Pa. The calcium oxide powder is characterized in that the water vapor adsorption amount below is 200 ml / g or more.
　ここで、粒度分布（Ｄ９０）が１～８μｍの範囲内であることが好ましい。 Here, the particle size distribution (D90) is preferably in the range of 1 to 8 μm.
　また、本発明は、上記のいずれかに記載の酸化カルシウム粉末を含有することを特徴とする吸着剤である。 Further, the present invention is an adsorbent characterized by containing the calcium oxide powder described in any of the above.
　また、本発明は、５００～７００℃の範囲内の条件下で水酸化カルシウムを大気中で焼成して酸化カルシウムを生成する焼成工程と、前記酸化カルシウムを粉末状に粉砕する粉砕工程と、を備えることを特徴とする酸化カルシウム粉末の製造方法である。 The present invention also includes a firing step in which calcium hydroxide is fired in the air under conditions within a range of 500 to 700 ° C. to generate calcium oxide, and a pulverizing step in which the calcium oxide is pulverized into a powder. It is a manufacturing method of the calcium oxide powder characterized by providing.
　ここで、前記粉末状の前記酸化カルシウムを分級する分級工程をさらに備えることが好ましい。 Here, it is preferable to further include a classification step of classifying the powdered calcium oxide.
　本発明によれば、粒子が微小であり、水分及び酸性ガスの吸着性に優れた酸化カルシウム粉末及び吸着剤並びに酸化カルシウム粉末の製造方法を提供することが可能となる。 According to the present invention, it is possible to provide a calcium oxide powder, an adsorbent, and a method for producing calcium oxide powder that have fine particles and are excellent in moisture and acid gas adsorption.
１．酸化カルシウム粉末（吸着剤）
　本発明の酸化カルシウム粉末は、平均粒子径が１０μｍ以下であり、ＢＥＴ比表面積１０～３０ｍ２／ｇの範囲内であり、塩基度が２５～１００μｍｏｌ／ｍ２の範囲内であり、水蒸気圧１００Ｐａの条件下における水蒸気吸着量が２００ｍｌ／ｇ以上である。 1. Calcium oxide powder (adsorbent)
The calcium oxide powder of the present invention has an average particle size of 10 μm or less, a BET specific surface area of 10 to 30 m 2 / g, a basicity of 25 to 100 μmol / m 2 , and a water vapor pressure of 100 Pa. The amount of water vapor adsorption under the above conditions is 200 ml / g or more.
　酸化カルシウム粉末の平均粒子径は、１０μｍ以下であり、好ましくは５μｍ以下であり、より好ましくは３μｍ以下である。酸化カルシウム粉末の平均粒子径が１０μｍを上回ると、粒径が大きくなりすぎるため、小型の電子機器や断熱材等には不向きとなりやすいほか、塗布や充填物として使用した際に外観が悪くなりやすい。酸化カルシウム粉末の平均粒子径の下限は、特に制限はないが、通常は１０ｎｍ以上である。平均粒子径が１０ｎｍを下回る酸化カルシウム粉末は製造が困難であるほか、粒径が小さすぎて取り扱いが困難となりやすい。 The average particle diameter of the calcium oxide powder is 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less. When the average particle size of the calcium oxide powder exceeds 10 μm, the particle size becomes too large, so it is not suitable for small electronic devices and heat insulating materials, and the appearance is likely to deteriorate when used as a coating or filling material. . The lower limit of the average particle diameter of the calcium oxide powder is not particularly limited, but is usually 10 nm or more. Calcium oxide powder having an average particle diameter of less than 10 nm is difficult to produce, and the particle diameter is too small to be easily handled.
　酸化カルシウム粉末のＢＥＴ比表面積は、１０～３０ｍ２／ｇの範囲内であり、好ましくは１２～２５ｍ２／ｇの範囲内であり、より好ましくは１５～２０ｍ２／ｇの範囲内である。酸化カルシウム粉末のＢＥＴ比表面積が１０ｍ２／ｇを下回ると、水分や酸性ガスの吸着速度が遅くなる傾向がある。一方、酸化カルシウム粉末のＢＥＴ比表面積が３０ｍ２／ｇを上回ると水分や酸性ガスの吸着速度が速すぎて取り扱いが困難になりやすい。したがって、酸化カルシウム粉末のＢＥＴ比表面積が１０～３０ｍ２／ｇの範囲内であると、水分や酸性ガスの吸着速度が適切であり、かつ取り扱い性が良好となる。 The BET specific surface area of the calcium oxide powder is in the range of 10 to 30 m 2 / g, preferably in the range of 12 to 25 m 2 / g, and more preferably in the range of 15 to 20 m 2 / g. When the BET specific surface area of the calcium oxide powder is less than 10 m 2 / g, the adsorption rate of moisture and acid gas tends to be slow. On the other hand, when the BET specific surface area of the calcium oxide powder exceeds 30 m 2 / g, the adsorption rate of moisture and acid gas is too high and the handling tends to be difficult. Accordingly, when the BET specific surface area of the calcium oxide powder is within the range of 10 to 30 m 2 / g, the adsorption rate of moisture and acid gas is appropriate, and the handleability is good.
　酸化カルシウム粉末の塩基度は、２５～１００μｍｏｌ／ｍ２の範囲内であり、好ましくは２８～５０μｍｏｌ／ｍ２の範囲内であり、より好ましくは３０～４０μｍｏｌ／ｍ２の範囲内である。酸化カルシウム粉末の塩基度が２５μｍｏｌ／ｍ２を下回ると、酸性ガスの吸着速度が遅くなる傾向がある。一方、酸化カルシウム粉末の塩基度が１００μｍｏｌ／ｍ２を上回ると、酸性ガスの吸着速度が速すぎて取り扱いが困難になりやすい。したがって、酸化カルシウム粉末の塩基度が２５～１００μｍｏｌ／ｍ２の範囲内であると、酸性ガスの吸着速度が適切であり、かつ取り扱い性が良好となる。ここで言う塩基度は、酸化カルシウムの比表面積１ｍ２/ｇあたりの二酸化炭素吸着量で定義され、後述する実施例に記載された方法あるいはこれに準じた方法で測定した値を意味する。 The basicity of the calcium oxide powder is in the range of 25 to 100 μmol / m 2 , preferably in the range of 28 to 50 μmol / m 2 , and more preferably in the range of 30 to 40 μmol / m 2 . When the basicity of the calcium oxide powder is less than 25 μmol / m 2 , the acid gas adsorption rate tends to be slow. On the other hand, when the basicity of the calcium oxide powder exceeds 100 μmol / m 2 , the acid gas adsorption rate is too high, and the handling tends to be difficult. Therefore, when the basicity of the calcium oxide powder is in the range of 25 to 100 μmol / m 2 , the acid gas adsorption rate is appropriate and the handleability is good. The basicity mentioned here is defined by the amount of carbon dioxide adsorbed per 1 m 2 / g of the specific surface area of calcium oxide, and means a value measured by the method described in the examples described later or a method according thereto.
　酸化カルシウム粉末の水蒸気圧１００Ｐａの条件下における水蒸気吸着量は、２００ｍｌ／ｇ以上であり、好ましくは２３０ｍｌ／ｇ以上であり、より好ましくは２５０ｍｌ／ｇ以上である。上記の水蒸気吸着量が２００ｍｌ／ｇを下回ると、吸水量が小さくて吸湿性能が低い。上記の水蒸気吸着量の上限は、特に制限はないが、通常は５０００ｍｌ／ｇ以下であり、１０００ｍｌ／ｇ以下であり、５００ｍｌ／ｇ以下である。 The water vapor adsorption amount of the calcium oxide powder under a water vapor pressure of 100 Pa is 200 ml / g or more, preferably 230 ml / g or more, more preferably 250 ml / g or more. When the water vapor adsorption amount is less than 200 ml / g, the water absorption amount is small and the moisture absorption performance is low. The upper limit of the water vapor adsorption amount is not particularly limited, but is usually 5000 ml / g or less, 1000 ml / g or less, and 500 ml / g or less.
　酸化カルシウム粉末の粒度分布における９０％粒径（粒度の小さいものから累積９０％における粒径：「Ｄ９０」）は、特に制限はないが、通常は１～８μｍの範囲内であり、好ましくは２～７μｍの範囲内であり、より好ましくは３～６μｍの範囲内である。酸化カルシウム粉末のＤ９０が８μｍを上回ると、粒径が大きくなりすぎるため、小型の電子機器や断熱材等には不向きとなりやすいほか、塗布や充填物として使用した際に外観が悪くなりやすい。酸化カルシウム粉末のＤ９０が１μｍを下回ると、製造が困難であるほか、粒径が小さすぎて取り扱いが困難となりやすい。 The 90% particle size in the particle size distribution of the calcium oxide powder (particle size from small particle size to cumulative 90% particle size: “D90”) is not particularly limited, but is usually in the range of 1 to 8 μm, preferably 2 It is in the range of ˜7 μm, more preferably in the range of 3 to 6 μm. When the D90 of the calcium oxide powder exceeds 8 μm, the particle size becomes too large, so that it tends to be unsuitable for small electronic devices, heat insulating materials, etc., and the appearance tends to deteriorate when used as a coating or filling material. When the D90 of the calcium oxide powder is less than 1 μm, it is difficult to produce, and the particle size is too small to be easily handled.
　本発明の酸化カルシウム粉末は、表面が被覆されることなく酸化カルシウムが直接外気と接し、高いＢＥＴ比表面積と塩基度を併せ持っているため、特に低密度（低圧）の水分や酸性ガスを効果的に吸収することができる。また、本発明の酸化カルシウム粉末は、平均粒子径が小さく微粉化されているため、電子機器や断熱材の小型化・薄膜化に対応できる。 In the calcium oxide powder of the present invention, calcium oxide is in direct contact with the outside air without being coated on the surface, and has a high BET specific surface area and basicity, so that low density (low pressure) moisture and acid gas are particularly effective. Can be absorbed into. In addition, since the calcium oxide powder of the present invention has a small average particle size and is pulverized, it can cope with downsizing and thinning of electronic devices and heat insulating materials.
　本発明の酸化カルシウム粉末は、特に真空断熱材の吸湿剤、酸性ガスの吸着剤としての用途に特に適している。真空断熱材とは、袋状に加工したラミネートフィルム内に芯材を収納したのちにラミネートフィルム内を減圧して密封した断熱材である。ラミネートフィルム内に空気や水分が侵入すると断熱性が低下するが、本発明の酸化カルシウム粉末をラミネートフィルム内に配合することで、空気や水分の侵入を防止しつつ酸化カルシウム粉末に起因するガスの発生が無いため、断熱性を高い状態で維持することができる。 The calcium oxide powder of the present invention is particularly suitable for use as a hygroscopic agent for a vacuum heat insulating material and an adsorbent for an acidic gas. The vacuum heat insulating material is a heat insulating material in which a core material is stored in a laminated film processed into a bag shape and then the inside of the laminated film is decompressed and sealed. When air or moisture penetrates into the laminate film, the heat insulating property is lowered.However, by blending the calcium oxide powder of the present invention into the laminate film, the gas caused by the calcium oxide powder is prevented while preventing the entry of air and moisture. Since there is no generation | occurrence | production, heat insulation can be maintained in a high state.
　特に、本発明の酸化カルシウム粉末は、有機ＥＬ等の電子機器の吸湿剤、酸性ガスの吸着剤に適している。例えば、本発明の酸化カルシウム粉末は、合成樹脂に分散させて、シート状、ペレット状、板状、フィルム状に成形して利用することができる。これらの成形物は、有機ＥＬディスプレイなどの電子機器用の乾燥剤として有利に使用することができる。合成樹脂には、ポリオレフィン樹脂、ポリアクリル樹脂、ポリアクリルニトリル樹脂、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、ポリカーボネート樹脂及びフッ素樹脂を用いることができる。また、本発明の酸化カルシウム粉末は、通常の吸湿剤に用いられている透湿性の袋や容器に収容して使用することもできる。このようにすることで、樹脂中を透過するわずかな水分や酸性ガスを酸化カルシウム粉末で効果的に吸着できる。なお、酸化カルシウム粉末は、単独で使用してもよいし、他の吸湿性材料（例えば、シリカゲルやモレキュラーシーブ）と併用してもよい。 In particular, the calcium oxide powder of the present invention is suitable as a hygroscopic agent for electronic devices such as organic EL and an adsorbent for acidic gas. For example, the calcium oxide powder of the present invention can be used after being dispersed in a synthetic resin and formed into a sheet, pellet, plate, or film. These molded products can be advantageously used as a desiccant for electronic devices such as organic EL displays. As the synthetic resin, polyolefin resin, polyacrylic resin, polyacrylonitrile resin, polyamide resin, polyester resin, epoxy resin, polycarbonate resin, and fluorine resin can be used. In addition, the calcium oxide powder of the present invention can be used by being housed in a moisture-permeable bag or container used in a normal hygroscopic agent. By doing in this way, the slight water | moisture content and acidic gas which permeate | transmit the inside of resin can be effectively adsorb | sucked with a calcium oxide powder. The calcium oxide powder may be used alone or in combination with other hygroscopic materials (for example, silica gel or molecular sieve).
　本発明の酸化カルシウムは、粉末状のまま用いてもよく、あるいは任意の形状に成形して使用してもよい。また、本発明の酸化カルシウムを適当な溶媒や高分子材料に充填した塗料、高分子材料に充填したテープやフィルムなどとして使用することができる。このため、有機ＥＬ、液晶等の水分を忌避する電子デバイス用乾燥剤、冷蔵庫・二重ガラスなどの断熱層用乾燥剤、バリアフィルムの水分吸着層、密閉容器のパッキン用（化学品、医薬品、食品の劣化防止）、真空配管の内面塗布用、Ｏリング用（高真空維持）などにも好適に使用することができる。 Calcium oxide of the present invention may be used as it is in powder form or may be used after being formed into an arbitrary shape. Further, it can be used as a paint filled with an appropriate solvent or polymer material of the calcium oxide of the present invention, a tape or a film filled with a polymer material, and the like. For this reason, desiccants for electronic devices that repel moisture such as organic EL and liquid crystals, desiccants for heat insulation layers such as refrigerators and double glass, moisture adsorption layers for barrier films, and packing for sealed containers (chemicals, pharmaceuticals, It can also be suitably used for food deterioration prevention), application to the inner surface of vacuum piping, O-ring use (maintaining high vacuum), and the like.
２．酸化カルシウムの製造方法
　本発明の酸化カルシウムの製造方法は、５００～７００℃の範囲内の条件下で水酸化カルシウムを大気中で焼成して酸化カルシウムを生成する焼成工程と、焼成工程で得られた酸化カルシウムを粉末状に粉砕する粉砕工程と、さらに必要に応じて粉末工程で得られた粉末状の酸化カルシウムを分級する分級工程を備える。 2. Calcium oxide production method The calcium oxide production method of the present invention is obtained by a calcining step in which calcium hydroxide is calcined in the air under conditions within a range of 500 to 700 ° C. to generate calcium oxide, and the calcining step. A pulverizing step of pulverizing the calcium oxide in powder form, and a classification step of classifying the powdered calcium oxide obtained in the powder step as necessary.
（１）焼成工程
　焼成工程は、原料となる水酸化カルシウムを焼成し、酸化カルシウムを生成する工程である。水酸化カルシウム（消石灰）の種類や製造方法は、特に制限なく、例えば酸化カルシウムに水を加えて水和したものなどを使用することができる。 (1) Firing step The firing step is a step of firing calcium hydroxide as a raw material to generate calcium oxide. There is no restriction | limiting in particular in the kind and manufacturing method of calcium hydroxide (slaked lime), For example, what added water to calcium oxide and hydrated etc. can be used.
　焼成工程は、５００～７００℃の範囲内の高温で、かつ大気中で行う。焼成温度が５００℃を下回ると、焼成が不十分で得られる酸化カルシウム粉末の結晶性が低くなり、水分や酸性ガスの吸着性が低くなりやすい。一方、焼成温度が７００℃を上回ると、ＢＥＴ比表面積が小さくなり、水分や酸性ガスの吸着性が低くなりやすい。焼成時間は、特に制限はないが、通常は３０分～３０時間の範囲内である。 The firing step is performed at a high temperature in the range of 500 to 700 ° C. and in the air. When the firing temperature is lower than 500 ° C., the crystallinity of the calcium oxide powder obtained due to insufficient firing is lowered, and the adsorptivity of moisture and acid gas tends to be lowered. On the other hand, when the firing temperature exceeds 700 ° C., the BET specific surface area becomes small, and the adsorptivity of moisture and acid gas tends to be low. The firing time is not particularly limited, but is usually in the range of 30 minutes to 30 hours.
　焼成工程は、大気中、すなわち、空気中かつ大気圧（約０．１ＭＰａ）で焼成を行う。このように、焼成工程を大気中で行うことにより、生成する酸化カルシウムの結晶性が高く、その結果、塩基度が高くて酸性ガスの吸着性が優れたものとなる。また、大気中で焼成工程を行うことで、真空焼成を行う場合と比較して、低コストで焼成を行うこともできる。 In the firing step, firing is performed in air, that is, in air and at atmospheric pressure (about 0.1 MPa). Thus, by performing a baking process in air | atmosphere, the crystallinity of the calcium oxide to produce | generate is high, As a result, the basicity is high and the adsorptivity of acidic gas becomes excellent. In addition, by performing the baking process in the air, baking can be performed at a lower cost than in the case of performing vacuum baking.
（２）粉砕工程
　粉砕工程は、焼成工程で得られた酸化カルシウムを粉末状に粉砕する工程である。焼成後に粉砕を行うことにより、粒子径が小さく、かつＢＥＴ比表面積が高い酸化カルシウム粉末を製造することができる。 (2) Crushing step The crushing step is a step of crushing calcium oxide obtained in the firing step into a powder form. By performing pulverization after firing, a calcium oxide powder having a small particle diameter and a high BET specific surface area can be produced.
　粉砕の方法は、特に限定されないが、メディアミル、回転ボールミル、振動ボールミル、遊星ボールミル、ロッキングミル、ペイントシェーカー、気流式粉砕機などの粉砕装置を使用することができる。粉砕装置の中で好ましいものは、気流式粉砕機であり、特に、微細かつシャープな粒度分布の粉体が得られることから、ジェットミルが好ましい。酸化カルシウム粉末の粒度分布がシャープであると、酸化カルシウム粉末の吸湿速度が安定化するため好ましい。なお、ジェットミルでの粉砕条件としては、例えば窒素やアルゴンなどの不活性ガス雰囲気下で、原料供給速度５ｋｇ／ｈにおいては、粉砕圧力を、０．３～１．５ＭＰａ、より好ましくは０．３～１．０ＭＰａにすることが好ましい。 The pulverization method is not particularly limited, and a pulverizer such as a media mill, a rotating ball mill, a vibration ball mill, a planetary ball mill, a rocking mill, a paint shaker, and an airflow pulverizer can be used. Among the pulverizers, an airflow pulverizer is preferable, and a jet mill is particularly preferable because a fine and sharp powder having a particle size distribution can be obtained. A sharp particle size distribution of the calcium oxide powder is preferable because the moisture absorption rate of the calcium oxide powder is stabilized. The pulverization conditions in the jet mill are, for example, in an inert gas atmosphere such as nitrogen or argon, and at a raw material supply rate of 5 kg / h, the pulverization pressure is 0.3 to 1.5 MPa, more preferably 0. It is preferably 3 to 1.0 MPa.
（３）分級工程
　粉砕工程後の酸化カルシウムは、必要に応じて分級することが好ましい。分級工程は、適度な目開きの篩などを用いて行うことができる。分級工程では、酸化カルシウムの平均粒子径が１０μｍ以下となるように行い、さらに、粒度分布（Ｄ９０）が１～８μｍの範囲内となるように粒度分布を調整することが好ましい。 (3) Classification process It is preferable to classify the calcium oxide after a grinding | pulverization process as needed. The classification step can be performed using a sieve with an appropriate opening. In the classification step, the average particle diameter of calcium oxide is preferably 10 μm or less, and the particle size distribution is preferably adjusted so that the particle size distribution (D90) is in the range of 1 to 8 μm.
　以下、本発明を実施例に基づいて具体的に説明するが、これらは本発明の目的を限定するものではなく、また、本発明は、これら実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but these do not limit the object of the present invention, and the present invention is not limited to these examples.
［ＢＥＴ比表面積の測定方法］
　ＢＥＴ比表面積の測定は、Ｍｏｎｏｓｏｒｂ（Ｑｕａｎｔａｃｈｒｏｍｅ　Ｉｎｓｔｒｕｍｅｎｔｓ製）を用いてＢＥＴ一点法により測定した。 [Measurement method of BET specific surface area]
The BET specific surface area was measured by the BET single point method using Monosorb (manufactured by Quantachrome Instruments).
［塩基度の測定方法］
　二酸化炭素の吸着量は昇温式脱離吸着過程測定（ＣＯ２－ＴＰＤ）法を測定して１ｇあたりの二酸化炭素吸着量を算出し、下記の式により、塩基度を換算した。二酸化炭素の昇温式脱離吸着過程測定（ＣＯ２－ＴＰＤ）は、ＢＥＬＣＡＴ－Ｂ（日本ベル株式会社製）を用いて測定した。
　塩基度（μｍｏｌ／ｍ２）＝　１ｇあたりの二酸化炭素吸着量（μｍｏｌ／ｇ）／比表面積（ｍ２／ｇ）　　　・・・式 [Measurement method of basicity]
The amount of carbon dioxide adsorbed was measured by the temperature rising desorption adsorption process measurement (CO 2 -TPD) method to calculate the amount of carbon dioxide adsorbed per gram, and the basicity was converted by the following formula. The temperature rising desorption adsorption process measurement (CO 2 -TPD) of carbon dioxide was measured using BELCAT-B (manufactured by Nippon Bell Co., Ltd.).
Basicity (μmol / m 2 ) = carbon dioxide adsorption per gram (μmol / g) / specific surface area (m 2 / g) Formula
［水蒸気吸着量の測定方法］
　水蒸気吸着量は、高精度全自動ガス吸着装置　ＢＥＬＳＯＲＰ１８（日本ベル株式会社製）を用いて水蒸気吸着等温線を測定し、水蒸気圧１００Ｐａでの酸化カルシウム１ｇあたりの水分吸着量（ｍｌ／ｇ）を測定した。水分吸着量は、標準状態（０℃、１気圧）における気体の体積に換算した値である。 [Measurement method of water vapor adsorption]
The water vapor adsorption amount is determined by measuring the water vapor adsorption isotherm using a highly accurate fully automatic gas adsorption device BELSORP18 (manufactured by Nippon Bell Co., Ltd.) and calculating the water adsorption amount (g / g) per 1 g of calcium oxide at a water vapor pressure of 100 Pa It was measured. The moisture adsorption amount is a value converted into a gas volume in a standard state (0 ° C., 1 atm).
［平均粒子径及び粒度分布（Ｄ９０）の測定方法］
試料の分散溶媒としてエタノールを使用し、超音波ホモジナイザー（ＭＯＤＥＬ　ＵＳ－１５０Ｔ、（株）日本精機製作所製）で３分間分散処理を行った。分散させた試料をレーザー回析法粒度分布分析装置（ＭＩＣＲＯＴＲＡＣ　ＨＲＡ９３２０－Ｘ１００、日機装（株）製）を用いて平均粒子径と粒度分布（Ｄ９０）とをそれぞれ測定した。 [Measuring method of average particle size and particle size distribution (D90)]
Ethanol was used as a dispersion solvent for the sample, and dispersion treatment was performed for 3 minutes with an ultrasonic homogenizer (MODEL US-150T, manufactured by Nippon Seiki Seisakusho Co., Ltd.). The dispersed sample was measured for the average particle size and particle size distribution (D90) using a laser diffraction particle size distribution analyzer (MICROTRAC HRA9320-X100, manufactured by Nikkiso Co., Ltd.).
［実施例１］
　水酸化カルシウム微粉末（ＣＨ－２Ｎ　宇部マテリアルズ株式会社製）を大気中で６００℃、１０時間焼成し、窒素雰囲気下ジェットミル（ＳＴＪ－２００　株式会社セイシン企業製）を用いて供給量５ｋｇ／ｈ、圧力０．７ＭＰａの条件で粉砕して酸化カルシウム粉末を得た。得られた酸化カルシウム粉末のＢＥＴ比表面積は１７．０ｍ２／ｇであり、塩基度は４５．９μｍｏｌ／ｍ２であった。水蒸気吸着量は、水蒸気圧１００Ｐａで２６５ｍｌ／ｇであった。また、平均粒子径は１．８μｍ、Ｄ９０は３．１μｍであった。その結果を表１に示す。 [Example 1]
Calcium hydroxide fine powder (CH-2N Ube Materials Co., Ltd.) is fired in the atmosphere at 600 ° C. for 10 hours, and supplied in a nitrogen atmosphere using a jet mill (STJ-200 Seisin Enterprise Co., Ltd.) 5 kg / h, The powder was pulverized under the pressure of 0.7 MPa to obtain calcium oxide powder. The obtained calcium oxide powder had a BET specific surface area of 17.0 m 2 / g and a basicity of 45.9 μmol / m 2 . The water vapor adsorption amount was 265 ml / g at a water vapor pressure of 100 Pa. The average particle size was 1.8 μm, and D90 was 3.1 μm. The results are shown in Table 1.
［実施例２］
　水酸化カルシウム微粉末（ＣＨ－２Ｎ　宇部マテリアルズ株式会社製）を大気中で６００℃、１０時間焼成し、窒素雰囲気下ジェットミル（ＳＴＪ－２００　株式会社セイシン企業製）を用いて供給量２ｋｇ／ｈ、圧力０．７ＭＰａの条件で粉砕して酸化カルシウム粉末を得た。得られた酸化カルシウム粉末のＢＥＴ比表面積は１６．８ｍ２／ｇであり、塩基度は３６．５μｍｏｌ／ｍ２であった。水蒸気吸着量は、水蒸気圧１００Ｐａで２３２ｍｌ／ｇであった。また、平均粒子径は１．８μｍ、Ｄ９０は３．２μｍであった。その結果を表１に示す。 [Example 2]
Calcium hydroxide fine powder (CH-2N Ube Materials Co., Ltd.) is calcined in the atmosphere at 600 ° C. for 10 hours and supplied in a nitrogen atmosphere using a jet mill (STJ-200 Seisin Enterprise Co., Ltd.). h, The powder was pulverized under the pressure of 0.7 MPa to obtain calcium oxide powder. The obtained calcium oxide powder had a BET specific surface area of 16.8 m 2 / g and a basicity of 36.5 μmol / m 2 . The water vapor adsorption amount was 232 ml / g at a water vapor pressure of 100 Pa. The average particle size was 1.8 μm, and D90 was 3.2 μm. The results are shown in Table 1.
［比較例１］
　水酸化カルシウム微粉末（ＣＨ－２Ｎ　宇部マテリアルズ株式会社製）を真空焼成炉に入れ、真空ポンプを用いて炉内圧力を６０Ｐａとした後、５００℃で４時間焼成して、酸化カルシウム粉末を得た。得られた酸化カルシウム粉末のＢＥＴ比表面積は６２．４ｍ２／ｇであり、塩基度は２４．４μｍｏｌ／ｍ２であった。水蒸気吸着量は、水蒸気圧１００Ｐａで１５５ｍｌ／ｇであった。また、平均粒子径は４．４μｍ、Ｄ９０は８．９μｍであった。その結果を表１に示す。 [Comparative Example 1]
Calcium hydroxide fine powder (CH-2N manufactured by Ube Materials Co., Ltd.) is placed in a vacuum firing furnace, and the furnace pressure is set to 60 Pa using a vacuum pump, followed by firing at 500 ° C. for 4 hours to obtain calcium oxide powder. Obtained. The obtained calcium oxide powder had a BET specific surface area of 62.4 m 2 / g and a basicity of 24.4 μmol / m 2 . The water vapor adsorption amount was 155 ml / g at a water vapor pressure of 100 Pa. The average particle size was 4.4 μm and D90 was 8.9 μm. The results are shown in Table 1.
［比較例２］
　水酸化カルシウム微粉末（ＣＨ－２Ｎ　宇部マテリアルズ株式会社製）を６００℃で１０時間焼成して酸化カルシウム粉末を得た（ジェットミル粉砕なし）。得られた酸化カルシウム粉末のＢＥＴ比表面積は１３．６ｍ２／ｇであり、塩基度は４７．８μｍｏｌ／ｍ２であった。水蒸気吸着量は、水蒸気圧１００Ｐａで１３１ｍｌ／ｇであった。また、平均粒子径は５．０μｍ、Ｄ９０は９．０μｍであった。その結果を表１に示す。 [Comparative Example 2]
Calcium hydroxide fine powder (CH-2N Ube Materials Co., Ltd.) was calcined at 600 ° C. for 10 hours to obtain calcium oxide powder (no jet mill pulverization). The obtained calcium oxide powder had a BET specific surface area of 13.6 m 2 / g and a basicity of 47.8 μmol / m 2 . The water vapor adsorption amount was 131 ml / g at a water vapor pressure of 100 Pa. Moreover, the average particle diameter was 5.0 micrometers and D90 was 9.0 micrometers. The results are shown in Table 1.
［比較例３］
　吸湿剤として市販されている粒状生石灰（ライスガード　宇部マテリアルズ株式会社製）を評価した。ＢＥＴ比表面積は１．５ｍ２／ｇであり、塩基度は１２０μｍｏｌ／ｍ２であった。水蒸気吸着量は、水蒸気圧１００Ｐａで０．１２ｍｌ／ｇであった。また、平均粒子径及びＤ９０は１０００μｍを超えていた。その結果を表１に示す。 [Comparative Example 3]
The granular quicklime (Riceguard Ube Materials Co., Ltd. product) marketed as a hygroscopic agent was evaluated. The BET specific surface area was 1.5 m 2 / g, and the basicity was 120 μmol / m 2 . The water vapor adsorption amount was 0.12 ml / g at a water vapor pressure of 100 Pa. Moreover, the average particle diameter and D90 were over 1000 micrometers. The results are shown in Table 1.
［比較例４：ＷＯ２０１４／１０９３３０号（特許文献３）の実施例３と同じ製造方法］
　水酸化カルシウム微粉末（ＣＨ－２Ｎ　宇部マテリアルズ株式会社製）を６００℃で１０時間焼成し、Ｎ－メチルピロリドンと窒素雰囲気下にて均一混合した後、窒素雰囲気下ジェットミル（ＳＴＪ－２００　株式会社セイシン企業製）を用いて供給量５ｋｇ／ｈ、圧力０．７ＭＰａの条件で粉砕して、粒子表面を有機溶媒で覆った酸化カルシウム粉末を得た。得られた酸化カルシウム粉末のＢＥＴ比表面積は１８．０ｍ２／ｇであり、塩基度は３８．３μｍｏｌ／ｍ２であった。水蒸気吸着量は、水蒸気圧１００Ｐａで７８ｍｌ／ｇであった。また、平均粒子径は１．１μｍ、Ｄ９０は３．１μｍであった。その結果を表１に示す。 [Comparative Example 4: Same manufacturing method as Example 3 of WO2014 / 109330 (Patent Document 3)]
Calcium hydroxide fine powder (CH-2N manufactured by Ube Materials Co., Ltd.) is calcined at 600 ° C. for 10 hours, uniformly mixed with N-methylpyrrolidone in a nitrogen atmosphere, and then jet milled in a nitrogen atmosphere (STJ-200 stock) Pulverized under the conditions of a supply rate of 5 kg / h and a pressure of 0.7 MPa to obtain a calcium oxide powder having the particle surface covered with an organic solvent. The obtained calcium oxide powder had a BET specific surface area of 18.0 m 2 / g and a basicity of 38.3 μmol / m 2 . The water vapor adsorption amount was 78 ml / g at a water vapor pressure of 100 Pa. The average particle size was 1.1 μm and D90 was 3.1 μm. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　以上の結果から、実施例１～２の酸化カルシウムは、塩基度が２５～１００μｍｏｌ／ｍ２の範囲内であることから酸性ガスの吸着性に優れ、かつ水蒸気圧１００Ｐａの条件下における水蒸気吸着量が２００ｍｌ／ｇ以上であることから水分の吸着性にも優れていることがわかった。一方、比較例１のように真空焼成したものは、実施例１～２と比べて、ＢＥＴ比表面積と粒径分布が大きく、塩基度と水蒸気吸着量において劣ることがわかった。また、比較例２のように粉砕工程のないものは、水蒸気吸着量に劣ることがわかった。さらに、比較例３の市販の乾燥剤は実施例１～３と比べて粒径が大きいことがわかった。さらにまた、比較例４のようにＮ－メチルピロリドンで表面処理したものは実施例１～３と比べて水蒸気吸着量において劣ることがわかった。 From the above results, the calcium oxides of Examples 1 and 2 have a basicity in the range of 25 to 100 μmol / m 2 , so that they have excellent acid gas adsorptivity and water vapor adsorption amount under the condition of water vapor pressure of 100 Pa. Was 200 ml / g or more, and it was found that the water adsorption was excellent. On the other hand, it was found that the vacuum fired product as in Comparative Example 1 had a larger BET specific surface area and particle size distribution than Examples 1 and 2, and was inferior in basicity and water vapor adsorption. Moreover, it turned out that the thing without a grinding | pulverization process like the comparative example 2 is inferior to water vapor | steam adsorption amount. Furthermore, the commercially available desiccant of Comparative Example 3 was found to have a larger particle size than Examples 1 to 3. Furthermore, it was found that the surface treated with N-methylpyrrolidone as in Comparative Example 4 was inferior in the water vapor adsorption amount as compared with Examples 1 to 3.

Claims (5)

  1. 　平均粒子径が１０μｍ以下であり、ＢＥＴ比表面積１０～３０ｍ２／ｇの範囲内であり、塩基度が２５～１００μｍｏｌ／ｍ２の範囲内であり、水蒸気圧１００Ｐａの条件下における水蒸気吸着量が２００ｍｌ／ｇ以上であることを特徴とする酸化カルシウム粉末。 The average particle diameter is 10 μm or less, the BET specific surface area is in the range of 10 to 30 m 2 / g, the basicity is in the range of 25 to 100 μmol / m 2 , and the water vapor adsorption amount under the condition of the water vapor pressure of 100 Pa is Calcium oxide powder characterized by being 200 ml / g or more.
  2. 　粒度分布（Ｄ９０）が１～８μｍの範囲内であることを特徴とする請求項１に記載の酸化カルシウム粉末。 2. The calcium oxide powder according to claim 1, wherein the particle size distribution (D90) is in the range of 1 to 8 μm.
  3. 　請求項１又は２に記載の酸化カルシウム粉末を含有することを特徴とする吸着剤。 An adsorbent comprising the calcium oxide powder according to claim 1 or 2.
  4. 　５００～７００℃の範囲内の条件下で水酸化カルシウムを大気中で焼成して酸化カルシウムを生成する焼成工程と、
    　前記酸化カルシウムを粉末状に粉砕する粉砕工程と、を備えることを特徴とする酸化カルシウム粉末の製造方法。     A calcining step in which calcium hydroxide is calcined in the air under conditions within a range of 500 to 700 ° C. to generate calcium oxide;
    And a pulverizing step of pulverizing the calcium oxide into a powder form.
  5. 　前記粉末状の前記酸化カルシウムを分級する分級工程をさらに備えることを特徴とする請求項４に記載の酸化カルシウム粉末の製造方法。 The method for producing calcium oxide powder according to claim 4, further comprising a classification step of classifying the powdered calcium oxide.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01308825A (en) * 1988-06-06 1989-12-13 Yoshizawa Sekkai Kogyo Kk Production of highly activated lime and unit therefor
JPH09268013A (en) * 1996-03-29 1997-10-14 Yoshizawa Sekkai Kogyo Kk Production of fine powder slaked lime by utilizing fluidized bed
JP2008001534A (en) * 2006-06-20 2008-01-10 Ube Material Industries Ltd Calcium oxide powder and method for producing the same
JP2013141656A (en) * 2012-01-12 2013-07-22 Yabashi Mine Parc Kk Moisture absorbent and method for producing the same
JP2014147927A (en) * 2013-01-10 2014-08-21 Ube Material Industries Ltd Moisture adsorbent and method for producing the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5165213U (en) 1974-11-20 1976-05-22
CN1035097A (en) * 1988-02-08 1989-08-30 重庆建筑工程学院 Use production of calcium oxide of high activity from calcium carbide residue
JP4264930B2 (en) * 2002-11-11 2009-05-20 岡山県共同石灰株式会社 Method for producing calcium oxide granules
JP2009215110A (en) * 2008-03-11 2009-09-24 Ube Ind Ltd Unslaked lime powder for expansive material, expansive material for concrete, water-hardening type binding material, concrete, and method of constructing concrete structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01308825A (en) * 1988-06-06 1989-12-13 Yoshizawa Sekkai Kogyo Kk Production of highly activated lime and unit therefor
JPH09268013A (en) * 1996-03-29 1997-10-14 Yoshizawa Sekkai Kogyo Kk Production of fine powder slaked lime by utilizing fluidized bed
JP2008001534A (en) * 2006-06-20 2008-01-10 Ube Material Industries Ltd Calcium oxide powder and method for producing the same
JP2013141656A (en) * 2012-01-12 2013-07-22 Yabashi Mine Parc Kk Moisture absorbent and method for producing the same
JP2014147927A (en) * 2013-01-10 2014-08-21 Ube Material Industries Ltd Moisture adsorbent and method for producing the same

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