KR20180117645A - Calcium oxide powder, adsorbent and method for producing calcium oxide powder - Google Patents
Calcium oxide powder, adsorbent and method for producing calcium oxide powder Download PDFInfo
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000292 calcium oxide Substances 0.000 title claims abstract description 98
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000000843 powder Substances 0.000 title claims abstract description 75
- 239000003463 adsorbent Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000010298 pulverizing process Methods 0.000 claims abstract description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 9
- 235000012255 calcium oxide Nutrition 0.000 description 85
- 238000001179 sorption measurement Methods 0.000 description 37
- 239000007789 gas Substances 0.000 description 24
- 239000002253 acid Substances 0.000 description 16
- 238000010304 firing Methods 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 235000011116 calcium hydroxide Nutrition 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002274 desiccant Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000012774 insulation material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—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
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- 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
Abstract
평균 입경이 10 ㎛ 이하이며, BET 비표면적 10∼30 ㎡/g의 범위 내이며, 염기도가 25∼100 ㎛ol/㎡의 범위 내이며, 수증기압 100 Pa의 조건하에서의 수증기 흡착량이 200 ml/g 이상인 것을 특징으로 하는 산화칼슘 분말이다. 이 경우에 있어서, 입도 분포(D90)가 1∼8 ㎛의 범위 내인 것이 바람직하다. 또한, 500∼700℃의 범위 내의 조건하에서 산화칼슘을 대기중에서 소성하는 공정과, 소성후의 산화칼슘을 분쇄하는 공정을 구비하는 것을 특징으로 하는 산화칼슘 분말의 제조 방법이다. 이 경우에 있어서, 분쇄후의 수산화칼슘을 분급하는 공정을 더 구비하는 것이 바람직하다.Wherein the average particle diameter is 10 占 퐉 or less and the BET specific surface area is in the range of 10 to 30 m2 / g, the basicity is in the range of 25 to 100 占 퐉 ol / m2 and the water vapor pressure is 100 ml / Wherein the calcium oxide powder is a calcium oxide powder. In this case, it is preferable that the particle size distribution D90 is in the range of 1 to 8 mu m. The present invention also provides a method for producing calcium oxide powder, which comprises a step of calcining calcium oxide in air at a temperature in the range of 500 to 700 占 폚, and a step of pulverizing calcined calcium oxide. In this case, it is preferable to further include a step of classifying the calcium hydroxide after the pulverization.
Description
본 발명은, 산화칼슘 분말 및 흡착제 및 산화칼슘 분말의 제조 방법에 관한 것이며, 특히, 수분이나 산성 가스의 흡착에 적합한 산화칼슘 분말 및 흡착제 및 산화칼슘 분말의 제조 방법에 관한 것이다. The present invention relates to a calcium oxide powder, 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 water or an acid gas and a method for producing calcium oxide powder.
종래, 생석회(산화칼슘)는, 흡습제, 탈수제, 염기성 로재, 시멘트 재료 등에 이용되고 있다. 특히, 최근에는, 물이나 산과의 높은 반응성을 이용하여, 유기 EL 디스플레이나 센서 등의 전자 기기나 진공 단열재에서의 수분의 흡착제(즉, 흡습제)나 산성 가스의 흡착제로서 이용하는 것이 검토되고 있다. 최근에는, 전자 기기ㆍ단열재의 소형화나 박막화에 따라, 미분화한 흡착제가 요구되고 있다. Background Art [0002] Conventionally, quicklime (calcium oxide) is used as a moisture absorbent, a dehydrating agent, a basic coating material, and a cement material. Particularly, in recent years, it has been studied to use water as an adsorbent (i.e., a desiccant) or an adsorbent for an acidic gas in electronic devices such as organic EL displays and sensors and vacuum insulators using high reactivity with water and acids. In recent years, there has been a demand for an undifferentiated adsorbent in accordance with the miniaturization and thinning of electronic devices and heat insulating materials.
예컨대, 특허문헌 1에는, BET 비표면적이 60 ㎡/g 이상이고, 직경 2∼100 nm의 범위에 있는 세공의 전체 세공 용적이 0.35 ml/g 이상이며, 입경이 0.25 mm 이하인 입자를 80 질량% 이상 함유하는 산화칼슘 분말이 개시되어 있다. 또한, 본 문헌에는, 수산화칼슘 분말을 300 Pa 이하의 압력하, 315∼500℃의 온도에서 소성함으로써, 반응성이 높은 산화칼슘 분말을 제조하는 방법도 개시되어 있다. For example, Patent Document 1 discloses that 80% by mass or less of particles having a BET specific surface area of 60 m < 2 > / g or more and a total pore volume of 0.35 ml / g or more and a particle diameter of 0.25 mm or less, Or more of calcium oxide powder. In addition, this document also discloses a method for producing calcium oxide powder having high reactivity by firing calcium hydroxide powder at a temperature of 315 to 500 캜 under a pressure of 300 Pa or less.
또한, 특허문헌 2에는, 온도 23℃, 상대 습도 45% RH의 조정된 대기중에 1시간 정치했을 때의 질량 증가량이, 1 ㎤당으로 환산하여 0.15 g 이상인 입상 생석회가 기재되어 있다. 또한, 본 문헌의 입상 생석회는, 입경이 0.075 mm 이상인 입자를 50 질량% 이상 포함하고, 입경이 1.0 mm 이상인 입자를 10 질량% 이상 포함하지 않는 것도 기재되어 있다. 또한, 본 문헌에는, 탭하지 않은 겉보기 부피 밀도가 0.5∼1.0 g/㎤의 범위에 있고, 또한 BET 비표면적이 10 ㎡/g 이상인 입상 소석회를, 300 Pa 이하의 압력하, 325∼500℃의 온도에서 1시간 이상 소성하는 입상 생석회의 제조 방법도 기재되어 있다. Patent Document 2 discloses a granular quicklime having a mass increase amount of 0.15 g or more calculated as 1 cm 3 when it is left standing for one hour in an atmosphere adjusted to a temperature of 23 캜 and a relative humidity of 45% RH. It is also described that the granulated quicklime of the present document contains 50 mass% or more of particles having a particle diameter of 0.075 mm or more and 10 mass% or more of particles having a particle diameter of 1.0 mm or more. The present document also discloses a process for producing a granulated slaked lime which has an untapped apparent bulk density of 0.5 to 1.0 g / cm 3 and a BET specific surface area of 10 m 2 / g or more at a pressure of 300 Pa or less at 325 to 500 캜 Also disclosed is a method for producing granular quicklime which is fired at a temperature for 1 hour or more.
또한, 특허문헌 3에는, 비프로톤성 극성 용매층을 갖는 산화칼슘 입자를 주성분으로 하고, 소수성과 높은 흡착 속도를 겸비한 수분 흡착제가 기재되어 있다. 또한, 본 문헌에 기재된 수분 흡착제의 BET 비표면적은 1∼100 ㎡/g이 바람직한 것, 평균 입경은 0.05∼10 ㎛이 바람직한 것이 기재되어 있다. 또한, 본 문헌에는, 산화칼슘을 비프로톤성 유기 용매 존재하에 미분화하는 수분 흡착제의 제조 방법도 기재되어 있다. Patent Document 3 discloses a moisture adsorbent having calcium oxide particles having an aprotic polar solvent layer as a main component and having hydrophobicity and a high adsorption rate. The BET specific surface area of the moisture adsorbent described in this document is preferably 1 to 100 m < 2 > / g, and the average particle diameter is preferably 0.05 to 10 mu m. In addition, this document also discloses a method for producing a water adsorbent for micronizing calcium oxide in the presence of an aprotic organic solvent.
특허문헌 1, 2에서는, 평균 입경이 비교적 크기 때문에, 입자의 미세화의 점에서 아직 개선의 여지가 있었다. 또한, 이들 문헌과 같이 진공 소성으로 제조한 산화칼슘은 결정성이 낮기 때문에, 물이나 산성 가스와의 화학 반응성이 낮아지기 쉽다.In Patent Documents 1 and 2, since the average particle size is relatively large, there is still room for improvement in terms of particle size reduction. In addition, as in these literatures, since calcium oxide produced by vacuum calcination is low in crystallinity, the chemical reactivity with water or an acid gas tends to be lowered.
특히, 전자 기기용이나 진공 단열재에서는, 저밀도의 수분이나 산성 가스를 흡착할 필요가 있기 때문에, 화학 반응성의 기여가 크고, 단순히 비표면적을 크게 한 것만으로는, 흡착 성능을 최적화하는 것이 어렵다. 또한, 산화칼슘 분말의 제조에 진공 소성로가 필요하기 때문에 고비용이 되기 쉬워, 비용면에서 개선의 여지가 있었다. Particularly, in electronic devices and vacuum insulation materials, since it is necessary to adsorb low-density moisture or acidic gas, it is difficult to optimize the adsorption performance only by making a large contribution of chemical reactivity and simply increasing the specific surface area. In addition, since a vacuum calcining furnace is required for the production of the calcium oxide powder, it is easy to increase the cost and there is room for improvement in cost.
특허문헌 3의 산화칼슘은, 흡착 성능이 뛰어나지만, 입자 표면에 피막된 비프로톤성 유기 용매가 기화함으로써, 전자 기기의 성능이나 진공 단열재 중의 진공도에 영향을 미칠 가능성이 있다. The calcium oxide of Patent Document 3 has excellent adsorption performance, but there is a possibility that the non-protonic organic solvent coated on the surface of the particles is vaporized, which may affect the performance of electronic equipment and the degree of vacuum in vacuum insulation.
본 발명의 목적은, 입자가 미세하고, 수분 및 산성 가스의 흡착성이 우수한 산화칼슘 분말 및 흡착제 및 산화칼슘 분말의 제조 방법을 제공하는 것에 있다. An object of the present invention is to provide a calcium oxide powder, an adsorbent, and a method for producing calcium oxide powder which are fine particles and excellent in adsorption of water and acid gas.
본 발명자들은, 이상의 목적을 달성하기 위해 예의 검토한 결과, 소정의 제조 방법으로 산화칼슘 분말을 제조함으로써, 입자가 미세하고, 수분 및 산성 가스의 흡착성이 우수한 산화칼슘 분말을 제조할 수 있는 것을 발견하여 본 발명을 완성했다.DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to attain the above object. As a result, they have found that calcium oxide powder having fine particles and excellent adsorption of water and acid gas can be produced by preparing calcium oxide powder by a predetermined manufacturing method Thereby completing the present invention.
즉, 본 발명은, 평균 입경이 10 ㎛ 이하이며, BET 비표면적 10∼30 ㎡/g의 범위 내이며, 염기도가 25∼100 ㎛ol/㎡의 범위 내이며, 수증기압 100 Pa의 조건하에서의 수증기 흡착량이 200 ml/g 이상인 것을 특징으로 하는 산화칼슘 분말이다. That is, the present invention relates to a process for producing a water-absorbing resin composition having an average particle diameter of 10 μm or less and a BET specific surface area in the range of 10 to 30 m 2 / g, a basicity within a range of 25 to 100 μmol / Is not less than 200 ml / g.
여기서, 입도 분포(D90)가 1∼8 ㎛의 범위 내인 것이 바람직하다. Here, it is preferable that the particle size distribution D90 is in the range of 1 to 8 mu m.
또한, 본 발명은, 상기 어느 하나에 기재된 산화칼슘 분말을 함유하는 것을 특징으로 하는 흡착제이다. Further, the present invention is an adsorbent characterized by containing the calcium oxide powder described in any one of the above-mentioned items.
또한, 본 발명은, 500∼700℃의 범위 내의 조건하에서 수산화칼슘을 대기중에서 소성하여 산화칼슘을 생성하는 소성 공정과, 상기 산화칼슘을 분말형으로 분쇄하는 분쇄 공정을 구비하는 것을 특징으로 하는 산화칼슘 분말의 제조 방법이다. The present invention also provides a method for producing calcium oxide, which comprises calcining step of calcining calcium hydroxide in the atmosphere under the condition of 500 to 700 占 폚 to produce calcium oxide, and crushing step of crushing the calcium oxide in powder form Powder.
여기서, 상기 분말형의 상기 산화칼슘을 분급하는 분급 공정을 더 구비하는 것이 바람직하다. Here, it is preferable to further include a classification step of classifying the powdery calcium oxide.
본 발명에 의하면, 입자가 미세하고, 수분 및 산성 가스의 흡착성이 우수한 산화칼슘 분말 및 흡착제 및 산화칼슘 분말의 제조 방법을 제공하는 것이 가능해진다. According to the present invention, it is possible to provide a calcium oxide powder, an adsorbent and a method for producing calcium oxide powder which are fine particles and excellent in the adsorption of moisture and acid gas.
1. 산화칼슘 분말(흡착제) 1. Calcium oxide powder (adsorbent)
본 발명의 산화칼슘 분말은, 평균 입경이 10 ㎛ 이하이며, BET 비표면적 10∼30 ㎡/g의 범위 내이며, 염기도가 25∼100 ㎛ol/㎡의 범위 내이며, 수증기압 100 Pa의 조건하에서의 수증기 흡착량이 200 ml/g 이상이다. The calcium oxide powder of the present invention preferably has a mean particle diameter of 10 mu m or less and a BET specific surface area in the range of 10 to 30 m2 / g, a basicity within a range of 25 to 100 mu mol / m & The amount of adsorption of water vapor is 200 ml / g or more.
산화칼슘 분말의 평균 입경은, 10 ㎛ 이하이며, 바람직하게는 5 ㎛ 이하이며, 보다 바람직하게는 3 ㎛ 이하이다. 산화칼슘 분말의 평균 입경이 10 ㎛을 상회하면, 입경이 지나치게 커지기 때문에, 소형의 전자 기기나 단열재 등에는 부적합해지기 쉬울 뿐만 아니라, 도포나 충전물로서 사용했을 때에 외관이 나빠지기 쉽다. 산화칼슘 분말의 평균 입경의 하한은, 특별히 제한은 없지만, 통상은 10 nm 이상이다. 평균 입경이 10 nm을 하회하는 산화칼슘 분말은 제조가 어려울 뿐만 아니라, 입경이 지나치게 작아 취급이 어려워지기 쉽다. The average particle diameter of the calcium oxide powder is 10 占 퐉 or less, preferably 5 占 퐉 or less, and more preferably 3 占 퐉 or less. If the average particle diameter of the calcium oxide powder is more than 10 占 퐉, the particle diameter becomes too large, which makes it unsuitable for small electronic apparatuses and heat insulating materials, and tends to deteriorate appearance when used as a coating or a 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 not only difficult to manufacture but also has a too small particle size, which makes handling difficult.
산화칼슘 분말의 BET 비표면적은, 10∼30 ㎡/g의 범위 내이며, 바람직하게는 12∼25 ㎡/g의 범위 내이며, 보다 바람직하게는 15∼20 ㎡/g의 범위 내이다. 산화칼슘 분말의 BET 비표면적이 10 ㎡/g을 하회하면, 수분이나 산성 가스의 흡착 속도가 느려지는 경향이 있다. 한편, 산화칼슘 분말의 BET 비표면적이 30 ㎡/g을 상회하면 수분이나 산성 가스의 흡착 속도가 지나치게 빨라 취급이 어려워지기 쉽다. 따라서, 산화칼슘 분말의 BET 비표면적이 10∼30 ㎡/g의 범위 내이면, 수분이나 산성 가스의 흡착 속도가 적절하고, 또한 취급성이 양호해진다. 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. If the BET specific surface area of the calcium oxide powder is less than 10 m < 2 > / g, the adsorption rate of water or acid gas tends to be slowed down. On the other hand, if the BET specific surface area of the calcium oxide powder is more than 30 m < 2 > / g, the adsorption rate of moisture or acidic gas becomes too fast, Therefore, if the BET specific surface area of the calcium oxide powder is in the range of 10 to 30 m < 2 > / g, the adsorption rate of water or acid gas is appropriate and the handling property is good.
산화칼슘 분말의 염기도는, 25∼100 ㎛ol/㎡의 범위 내이며, 바람직하게는 28∼50 ㎛ol/㎡의 범위 내이며, 보다 바람직하게는 30∼40 ㎛ol/㎡의 범위 내이다. 산화칼슘 분말의 염기도가 25 ㎛ol/㎡을 하회하면, 산성 가스의 흡착 속도가 느려지는 경향이 있다. 한편, 산화칼슘 분말의 염기도가 100 ㎛ol/㎡을 상회하면, 산성 가스의 흡착 속도가 지나치게 빨라 취급이 어려워지기 쉽다. 따라서, 산화칼슘 분말의 염기도가 25∼100 ㎛ol/㎡의 범위 내이면, 산성 가스의 흡착 속도가 적절하고, 또한 취급성이 양호해진다. 여기서 말하는 염기도는, 산화칼슘의 비표면적 1 ㎡/g당의 이산화탄소 흡착량으로 정의되며, 후술하는 실시예에 기재된 방법 혹은 이것에 준한 방법으로 측정한 값을 의미한다. The basicity of the calcium oxide powder is in the range of 25 to 100 占 퐉 ol / m2, preferably in the range of 28 to 50 占 퐉 ol / m2, more preferably in the range of 30 to 40 占 퐉 ol / m2. If the basicity of the calcium oxide powder is less than 25 μmol / m 2, the adsorption rate of the acid gas tends to be slowed down. On the other hand, if the basicity of the calcium oxide powder is more than 100 μmol / m 2, the adsorption rate of the acid gas is excessively high and the handling tends to become difficult. Therefore, if the basicity of the calcium oxide powder is in the range of 25 to 100 mu mol / m < 2 >, the adsorption rate of the acidic gas is appropriate and the handling property is good. The basicity referred to herein is defined as the amount of carbon dioxide adsorbed per 1 m2 / g of the specific surface area of calcium oxide, and means a value measured by the method described in the following Examples or a method similar thereto.
산화칼슘 분말의 수증기압 100 Pa의 조건하에서의 수증기 흡착량은, 200 ml/g 이상이며, 바람직하게는 230 ml/g 이상이며, 보다 바람직하게는 250 ml/g 이상이다. 상기 수증기 흡착량이 200 ml/g을 하회하면, 흡수량이 작아 흡습 성능이 낮다. 상기 수증기 흡착량의 상한은, 특별히 제한은 없지만, 통상은 5000 ml/g 이하이며, 1000 ml/g 이하이며, 500 ml/g 이하이다. The amount of water vapor adsorption under the condition of the water vapor pressure of 100 Pa of the calcium oxide powder is 200 ml / g or more, preferably 230 ml / g or more, and more preferably 250 ml / g or more. If the amount of water vapor adsorption is less than 200 ml / g, the water absorption amount is low and the moisture absorption performance is low. The upper limit of the amount of adsorption of water vapor is not particularly limited, but is usually 5000 ml / g or less, 1000 ml / g or less, and 500 ml / g or less.
산화칼슘 분말의 입도 분포에서의 90% 입경(입도가 작은 것부터 누적 90%에서의 입경 : 「D90」)은, 특별히 제한은 없지만, 통상은 1∼8 ㎛의 범위 내이며, 바람직하게는 2∼7 ㎛의 범위 내이며, 보다 바람직하게는 3∼6 ㎛의 범위 내이다. 산화칼슘 분말의 D90이 8 ㎛을 상회하면, 입경이 지나치게 커지기 때문에, 소형의 전자 기기나 단열재 등에는 부적합해지기 쉬울 뿐만 아니라, 도포나 충전물로서 사용했을 때에 외관이 나빠지기 쉽다. 산화칼슘 분말의 D90이 1 ㎛을 하회하면, 제조가 어려울 뿐만 아니라, 입경이 지나치게 작아 취급이 어려워지기 쉽다. The 90% particle diameter (particle diameter at a cumulative 90% from the small particle size: " D90 ") in the particle size distribution of the calcium oxide powder is not particularly limited, but is usually in the range of 1 to 8 탆, Preferably in the range of 3 to 7 mu m, and more preferably in the range of 3 to 6 mu m. If the D90 of the calcium oxide powder is more than 8 占 퐉, the particle diameter becomes excessively large, which makes it unsuitable for small electronic apparatuses and insulation materials, and is liable to deteriorate in appearance when used as a coating or a filling material. If the D90 of the calcium oxide powder is less than 1 占 퐉, it is not only difficult to manufacture, but also the particle diameter is too small to be easily handled.
본 발명의 산화칼슘 분말은, 표면이 피복되지 않아 산화칼슘이 직접 외기와 접하고, 높은 BET 비표면적과 염기도를 겸비하기 때문에, 특히 저밀도(저압)의 수분이나 산성 가스를 효과적으로 흡수할 수 있다. 또한, 본 발명의 산화칼슘 분말은, 평균 입경이 작고 미분화되어 있기 때문에, 전자 기기나 단열재의 소형화ㆍ박막화에 대응할 수 있다. The calcium oxide powder of the present invention does not cover the surface, calcium oxide directly contacts with the outside air, and has high BET specific surface area and basicity, so that it is possible to effectively absorb moisture and acid gas particularly at low density (low pressure). In addition, since the calcium oxide powder of the present invention has a small average particle diameter and is undifferentiated, it can cope with the miniaturization and thinning of electronic equipment and heat insulating materials.
본 발명의 산화칼슘 분말은, 특히 진공 단열재의 흡습제, 산성 가스의 흡착제로서의 용도에 특히 적합하다. 진공 단열재란, 주머니형으로 가공한 라미네이트 필름 내에 코어 재료를 수납한 후에 라미네이트 필름 내를 감압하여 밀봉한 단열재이다. 라미네이트 필름 내에 공기나 수분이 침입하면 단열성이 저하되지만, 본 발명의 산화칼슘 분말을 라미네이트 필름 내에 배합함으로써, 공기나 수분의 침입을 방지하면서 산화칼슘 분말에 기인하는 가스의 발생이 없기 때문에, 단열성을 높은 상태로 유지할 수 있다. The calcium oxide powder of the present invention is particularly suitable for use as a desiccant for a vacuum insulator and an adsorbent for an acidic gas. The vacuum insulation material is a heat insulation material in which a core material is contained in a laminated film processed into a bag-like shape, and then the inside of the laminated film is decompressed and sealed. When air or moisture enters the laminate film, the heat insulating property is lowered. However, since the calcium oxide powder of the present invention is incorporated into the laminate film, there is no generation of gas due to the calcium oxide powder while preventing intrusion of air or moisture, It can be maintained in a high state.
특히, 본 발명의 산화칼슘 분말은, 유기 EL 등의 전자 기기의 흡습제, 산성 가스의 흡착제에 적합하다. 예컨대, 본 발명의 산화칼슘 분말은, 합성 수지에 분산시켜, 시트형, 펠릿형, 판형, 필름형으로 성형하여 이용할 수 있다. 이들 성형물은, 유기 EL 디스플레이 등의 전자 기기용의 건조제로서 유리하게 사용할 수 있다. 합성 수지에는, 폴리올레핀 수지, 폴리아크릴 수지, 폴리아크릴니트릴 수지, 폴리아미드 수지, 폴리에스테르 수지, 에폭시 수지, 폴리카보네이트 수지 및 불소 수지를 이용할 수 있다. 또한, 본 발명의 산화칼슘 분말은, 통상의 흡습제에 이용되고 있는 투습성의 주머니나 용기에 수용하여 사용할 수도 있다. 이와 같이 함으로써, 수지 내를 투과하는 근소한 수분이나 산성 가스를 산화칼슘 분말로 효과적으로 흡착할 수 있다. 또, 산화칼슘 분말은, 단독으로 사용해도 좋고, 다른 흡습성 재료(예컨대, 실리카겔이나 몰레큘러 시브)와 병용해도 좋다. Particularly, the calcium oxide powder of the present invention is suitable as a desiccant for electronic equipment such as organic EL and an adsorbent for acidic gas. For example, the calcium oxide powder of the present invention can be dispersed in a synthetic resin and molded into a sheet, a pellet, a plate or a film. These molded products can be advantageously used as a drying agent for electronic devices such as organic EL displays. As the synthetic resin, a polyolefin resin, a polyacrylic resin, a polyacrylonitrile resin, a polyamide resin, a polyester resin, an epoxy resin, a polycarbonate resin and a fluororesin can be used. In addition, the calcium oxide powder of the present invention may be accommodated in a moisture-permeable bag or container used for ordinary moisture absorbent. By doing so, it is possible to effectively adsorb a small amount of moisture or acid gas permeating through the resin into the calcium oxide powder. The calcium oxide powder may be used singly or in combination with other hygroscopic materials (for example, silica gel or molecular sieve).
본 발명의 산화칼슘은, 분말형 그대로 이용해도 좋고, 혹은 임의의 형상으로 성형하여 사용해도 좋다. 또한, 본 발명의 산화칼슘을 적당한 용매나 고분자 재료에 충전한 도료, 고분자 재료에 충전한 테이프나 필름 등으로서 사용할 수 있다. 이 때문에, 유기 EL, 액정 등의 수분을 기피하는 전자 디바이스용 건조제, 냉장고ㆍ이중 유리 등의 단열층용 건조제, 배리어 필름의 수분 흡착층, 밀폐 용기의 패킹용(화학품, 의약품, 식품의 열화 방지), 진공 배관의 내면 도포용, O링용(고진공 유지) 등에도 적합하게 사용할 수 있다. The calcium oxide of the present invention may be used in the form of powder or may be molded into an arbitrary shape. Further, the calcium oxide of the present invention can be used as a coating material filled in a suitable solvent or polymer material, a tape or film filled in a polymer material, or the like. For this reason, a drying agent for an electronic device, a drying agent for a heat insulating layer such as a refrigerator and a double glass, a moisture adsorbing layer for a barrier film, a packing (for preventing deterioration of chemical products, medicines and foods) , For application to the inner surface of vacuum pipes, for O-rings (high vacuum maintenance), and the like.
2. 산화칼슘의 제조 방법 2. Manufacturing method of calcium oxide
본 발명의 산화칼슘의 제조 방법은, 500∼700℃의 범위 내의 조건하에서 수산화칼슘을 대기중에서 소성하여 산화칼슘을 생성하는 소성 공정과, 소성 공정에서 얻어진 산화칼슘을 분말형으로 분쇄하는 분쇄 공정과, 또한 필요에 따라서 분말 공정에서 얻어진 분말형의 산화칼슘을 분급하는 분급 공정을 구비한다. The method for producing calcium oxide according to the present invention comprises a calcination step of calcining calcium hydroxide in the atmosphere under the conditions within a range of 500 to 700 DEG C to produce calcium oxide, a crushing step of crushing the calcium oxide obtained in the calcination step into a powder form, And a classifying step of classifying the powdery calcium oxide obtained in the powder step as necessary.
(1) 소성 공정 (1) Firing process
소성 공정은, 원료가 되는 수산화칼슘을 소성하여 산화칼슘을 생성하는 공정이다. 수산화칼슘(소석회)의 종류나 제조 방법은 특별히 제한은 없고, 예컨대 산화칼슘에 물을 가하여 수화한 것 등을 사용할 수 있다. The firing step is a step of firing calcium hydroxide as a raw material to produce calcium oxide. The kind of the calcium hydroxide (slaked lime) and the production method thereof are not particularly limited, and for example, hydrated calcium hydroxide with water may be used.
소성 공정은, 500∼700℃의 범위 내의 고온 및 대기중에서 행한다. 소성 온도가 500℃를 하회하면, 소성이 불충분하여 얻어지는 산화칼슘 분말의 결정성이 낮아지고, 수분이나 산성 가스의 흡착성이 낮아지기 쉽다. 한편, 소성 온도가 700℃를 상회하면, BET 비표면적이 작아지고, 수분이나 산성 가스의 흡착성이 낮아지기 쉽다. 소성 시간은 특별히 제한은 없지만, 통상은 30분∼30시간의 범위 내이다. The firing step is carried out at a high temperature in the range of 500 to 700 DEG C and in the atmosphere. If the calcination temperature is lower than 500 캜, the calcination is insufficient, the crystallinity of the obtained calcium oxide powder is lowered, and the adsorption of water and acid gas tends to be lowered. On the other hand, if the firing temperature exceeds 700 ° C, the BET specific surface area becomes small and the adsorption of moisture and acid gas tends to be lowered. The firing time is not particularly limited, but is usually in the range of 30 minutes to 30 hours.
소성 공정은, 대기중, 즉, 공기중 및 대기압(약 0.1 MPa)에서 소성을 행한다. 이와 같이, 소성 공정을 대기중에서 행하는 것에 의해, 생성되는 산화칼슘의 결정성이 높고, 그 결과, 염기도가 높아 산성 가스의 흡착성이 우수한 것이 된다. 또한, 대기중에서 소성 공정을 행함으로써, 진공 소성을 행하는 경우와 비교하여 저비용으로 소성을 행할 수도 있다. The firing process is performed in the air, that is, in air and at atmospheric pressure (about 0.1 MPa). Thus, by carrying out the calcination step in the atmosphere, the produced calcium oxide has a high crystallinity, and as a result, it has a high basicity and is excellent in the adsorbability of the acid gas. Further, by carrying out the firing step in the atmosphere, the firing can be performed at a lower cost as compared with the case of performing the vacuum firing.
(2) 분쇄 공정 (2) Grinding process
분쇄 공정은, 소성 공정에서 얻어진 산화칼슘을 분말형으로 분쇄하는 공정이다. 소성후에 분쇄를 행하는 것에 의해, 입경이 작고, 또한 BET 비표면적이 높은 산화칼슘 분말을 제조할 수 있다. The pulverizing step is a step of pulverizing the calcium oxide obtained in the sintering step into a powder form. By pulverization after firing, a calcium oxide powder having a small particle diameter and a high BET specific surface area can be produced.
분쇄의 방법은 특별히 한정되지 않지만, 미디어밀, 회전볼밀, 진동볼밀, 유성볼밀, 로킹밀, 페인트쉐이커, 기류식 분쇄기 등의 분쇄 장치를 사용할 수 있다. 분쇄 장치 중에서 바람직한 것은 기류식 분쇄기이며, 특히, 미세하고 샤프한 입도 분포의 분체를 얻을 수 있다는 점에서, 제트밀이 바람직하다. 산화칼슘 분말의 입도 분포가 샤프하면, 산화칼슘 분말의 흡습 속도가 안정화되기 때문에 바람직하다. 또, 제트밀에서의 분쇄 조건으로는, 예컨대 질소나 아르곤 등의 불활성 가스 분위기하에서, 원료 공급 속도 5 kg/h에서는, 분쇄 압력을 0.3∼1.5 MPa, 보다 바람직하게는 0.3∼1.0 MPa로 하는 것이 바람직하다. The pulverizing method is not particularly limited, but a pulverizing apparatus such as a media mill, a rotating ball mill, a vibrating ball mill, a planetary ball mill, a locking mill, a paint shaker, an air stream type pulverizer and the like can be used. Among jet mills, jet mills are preferred, and jet mills are particularly preferable in that fine powder with sharp and sharp particle size distribution can be obtained. Sharpness of the 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 include setting the pulverization pressure at 0.3 to 1.5 MPa, more preferably 0.3 to 1.0 MPa at a raw material feed rate of 5 kg / h under an inert gas atmosphere such as nitrogen or argon desirable.
(3) 분급 공정 (3) Classification process
분쇄 공정후의 산화칼슘은, 필요에 따라서 분급하는 것이 바람직하다. 분급 공정은, 메시 크기가 적당한 체 등을 이용하여 행할 수 있다. 분급 공정에서는, 산화칼슘의 평균 입경이 10 ㎛ 이하가 되도록 행하고, 또한, 입도 분포(D90)가 1∼8 ㎛의 범위 내가 되도록 입도 분포를 조정하는 것이 바람직하다. The calcium oxide after the pulverizing step is preferably classified as necessary. The classification process can be performed using a sieve or the like having a suitable mesh size. In the classification step, it is preferable to adjust the particle size distribution such that the average particle diameter of calcium oxide is 10 m or less and the particle size distribution (D90) is in the range of 1 to 8 m.
실시예 Example
이하, 본 발명을 실시예에 기초하여 구체적으로 설명하지만, 이들은 본 발명의 목적을 한정하는 것은 아니며, 또한, 본 발명은 이들 실시예에 한정되는 것이 아니다. Hereinafter, the present invention will be described concretely on the basis of examples, but they should not be construed as limiting the object of the present invention, and the present invention is not limited to these examples.
[BET 비표면적의 측정 방법] [Method of measuring BET specific surface area]
BET 비표면적의 측정은, Monosorb(Quantachrome Instruments 제조)를 이용하여 BET 일점법에 의해 측정했다. The BET specific surface area was measured by the BET one-point method using Monosorb (manufactured by Quantachrome Instruments).
[염기도의 측정 방법] [Method of measuring basicity]
이산화탄소의 흡착량은 승온식 이탈 흡착 과정 측정(CO2-TPD)법을 측정하여 1 g당의 이산화탄소 흡착량을 산출하고, 하기의 식에 의해 염기도를 환산했다. 이산화탄소의 승온식 이탈 흡착 과정 측정(CO2-TPD)은, BELCAT-B(일본벨 주식회사 제조)를 이용하여 측정했다. The adsorption amount of carbon dioxide was measured by measuring the temperature rise type desorption adsorption process (CO 2 -TPD) method, and the amount of adsorbed carbon dioxide per 1 g was calculated, and the basicity was converted by the following equation. The measurement of the temperature elevation type desorption adsorption process (CO 2 -TPD) of carbon dioxide was measured using BELCAT-B (manufactured by Japan Bell Corporation).
염기도(㎛ol/㎡)=1 g당의 이산화탄소 흡착량(㎛ol/g)/비표면적(㎡/g)ㆍㆍㆍ식(Μmol / m 2) = amount of carbon dioxide adsorbed per 1 g (탆 ol / g) / specific surface area (m 2 / g)
[수증기 흡착량의 측정 방법] [Method of measuring amount of adsorption of water vapor]
수증기 흡착량은, 고정밀도 전자동 가스 흡착 장치 BELSORP18(일본벨 주식회사 제조)을 이용하여 수증기 흡착 등온선을 측정하고, 수증기압 100 Pa에서의 산화칼슘 1 g당의 수분 흡착량(ml/g)을 측정했다. 수분 흡착량은, 표준 상태(0℃, 1기압)에서의 기체의 체적으로 환산한 값이다. The water vapor adsorption isotherm was measured using a high-precision automatic gas adsorption apparatus BELSORP18 (manufactured by Japan Bell Co., Ltd.) and the amount of water adsorption (ml / g) per 1 g of calcium oxide at a water vapor pressure of 100 Pa was measured. The moisture adsorption amount is a value converted into the volume of the gas at the standard state (0 占 폚, 1 atm).
[평균 입경 및 입도 분포(D90)의 측정 방법] [Measurement method of average particle diameter and particle size distribution (D90)] [
시료의 분산 용매로서 에탄올을 사용하고, 초음파 호모게나이저(MODEL US-150T, (주)일본정기 제작소 제조)로 3분간 분산 처리를 행했다. 분산시킨 시료를 레이저 회절법 입도 분포 분석 장치(MICROTRAC HRA9320-X100, 니키소(주) 제조)를 이용하여 평균 입경과 입도 분포(D90)를 각각 측정했다. Ethanol was used as a dispersion solvent of the sample, and dispersion treatment was performed for 3 minutes with an ultrasonic homogenizer (MODEL US-150T, manufactured by JEOL Ltd.). The average particle size and the particle size distribution (D90) of the dispersed sample were measured using a laser diffraction particle size distribution analyzer (MICROTRAC HRA9320-X100, manufactured by Nikkiso Co., Ltd.).
[실시예 1] [Example 1]
수산화칼슘 미분말(CH-2N 우베마테리알즈 주식회사 제조)을 대기중에서 600℃, 10시간 소성하고, 질소 분위기하 제트밀(STJ-200 주식회사 세이신기업 제조)을 이용하여 공급량 5 kg/h, 압력 0.7 MPa의 조건으로 분쇄하여 산화칼슘 분말을 얻었다. 얻어진 산화칼슘 분말의 BET 비표면적은 17.0 ㎡/g이며, 염기도는 45.9 ㎛ol/㎡였다. 수증기 흡착량은, 수증기압 100 Pa에서 265 ml/g였다. 또한, 평균 입경은 1.8 ㎛, D90은 3.1 ㎛였다. 그 결과를 표 1에 나타낸다. (CH-2N Ube Industries Co., Ltd.) was fired in the air at 600 ° C for 10 hours, and a feed rate of 5 kg / h and a pressure of 0.7 kg / hr were measured using a jet mill (STJ- MPa to obtain a calcium oxide powder. The calcium oxide powder thus obtained had a BET specific surface area of 17.0 m < 2 > / g and a basicity of 45.9 mu mol / m < 2 >. The amount of water vapor adsorption was 265 ml / g at a water vapor pressure of 100 Pa. The average particle diameter was 1.8 占 퐉 and D90 was 3.1 占 퐉. The results are shown in Table 1.
[실시예 2] [Example 2]
수산화칼슘 미분말(CH-2N 우베마테리알즈 주식회사 제조)을 대기중에서 600℃, 10시간 소성하고, 질소 분위기하 제트밀(STJ-200 주식회사 세이신기업 제조)을 이용하여 공급량 2 kg/h, 압력 0.7 MPa의 조건으로 분쇄하여 산화칼슘 분말을 얻었다. 얻어진 산화칼슘 분말의 BET 비표면적은 16.8 ㎡/g이며, 염기도는 36.5 ㎛ol/㎡였다. 수증기 흡착량은, 수증기압 100 Pa에서 232 ml/g였다. 또한, 평균 입경은 1.8 ㎛, D90은 3.2 ㎛였다. 그 결과를 표 1에 나타낸다. (CH-2N Ube Industries, Ltd.) was baked at 600 ° C for 10 hours in the atmosphere, and a feed rate of 2 kg / h and a pressure of 0.7 kg / hr were measured using a jet mill (STJ-200 manufactured by Seishin Co., MPa to obtain a calcium oxide powder. The calcium oxide powder thus obtained had a BET specific surface area of 16.8 m 2 / g and a basicity of 36.5 μmol / m 2. The amount of water vapor adsorption was 232 ml / g at a water vapor pressure of 100 Pa. The average particle diameter was 1.8 占 퐉 and D90 was 3.2 占 퐉. The results are shown in Table 1.
[비교예 1] [Comparative Example 1]
수산화칼슘 미분말(CH-2N 우베마테리알즈 주식회사 제조)을 진공 소성로에 넣고, 진공 펌프를 이용하여 로내 압력을 60 Pa로 한 후, 500℃에서 4시간 소성하여, 산화칼슘 분말을 얻었다. 얻어진 산화칼슘 분말의 BET 비표면적은 62.4 ㎡/g이며, 염기도는 24.4 ㎛ol/㎡였다. 수증기 흡착량은, 수증기압 100 Pa에서 155 ml/g였다. 또한, 평균 입경은 4.4 ㎛, D90은 8.9 ㎛였다. 그 결과를 표 1에 나타낸다. The calcium hydroxide fine powder (CH-2N Ube Industries Co., Ltd.) was placed in a vacuum sintering furnace, and the furnace pressure was adjusted to 60 Pa by using a vacuum pump, followed by calcination at 500 占 폚 for 4 hours to obtain calcium oxide powder. The calcium oxide powder thus obtained had a BET specific surface area of 62.4 m 2 / g and a basicity of 24.4 μmol / m 2. The amount of water vapor adsorption was 155 ml / g at a water vapor pressure of 100 Pa. The average particle diameter was 4.4 占 퐉 and D90 was 8.9 占 퐉. The results are shown in Table 1.
[비교예 2] [Comparative Example 2]
수산화칼슘 미분말(CH-2N 우베마테리알즈 주식회사 제조)을 600℃에서 10시간 소성하여 산화칼슘 분말을 얻었다(제트밀 분쇄 없음). 얻어진 산화칼슘 분말의 BET 비표면적은 13.6 ㎡/g이며, 염기도는 47.8 ㎛ol/㎡였다. 수증기 흡착량은, 수증기압 100 Pa에서 131 ml/g였다. 또한, 평균 입경은 5.0 ㎛, D90은 9.0 ㎛였다. 그 결과를 표 1에 나타낸다. Calcium hydroxide fine powder (CH-2N Ube Industries Co., Ltd.) was calcined at 600 占 폚 for 10 hours to obtain a calcium oxide powder (without jet mill pulverization). The calcium oxide powder thus obtained had a BET specific surface area of 13.6 m 2 / g and a basicity of 47.8 μmol / m 2. The amount of water vapor adsorption was 131 ml / g at a water vapor pressure of 100 Pa. The average particle diameter was 5.0 mu m and D90 was 9.0 mu m. The results are shown in Table 1.
[비교예 3] [Comparative Example 3]
흡습제로서 시판되고 있는 입상 생석회(라이스가드 우베마테리알즈 주식회사 제조)를 평가했다. BET 비표면적은 1.5 ㎡/g이며, 염기도는 120 ㎛ol/㎡였다. 수증기 흡착량은, 수증기압 100 Pa에서 0.12 ml/g였다. 또한, 평균 입경 및 D90은 1000 ㎛을 초과했다. 그 결과를 표 1에 나타낸다. (Commercially available from Rice Guard Ube Industries, Ltd.) as a moisture absorbent. The BET specific surface area was 1.5 m 2 / g and the basicity was 120 탆 ol / m 2. The amount of water vapor adsorption was 0.12 ml / g at a water vapor pressure of 100 Pa. Also, the average particle diameter and D90 exceeded 1000 mu m. The results are shown in Table 1.
[비교예 4 : WO2014/109330호(특허문헌 3)의 실시예 3과 동일한 제조 방법] [Comparative Example 4: the same manufacturing method as in Example 3 of WO2014 / 109330 (Patent Document 3)] [
수산화칼슘 미분말(CH-2N 우베마테리알즈 주식회사 제조)을 600℃에서 10시간 소성하고, N-메틸피롤리돈과 질소 분위기하에서 균일 혼합한 후, 질소 분위기하 제트밀(STJ-200 주식회사 세이신기업 제조)을 이용하여 공급량 5 kg/h, 압력 0.7 MPa의 조건으로 분쇄하여, 입자 표면을 유기 용매로 덮은 산화칼슘 분말을 얻었다. 얻어진 산화칼슘 분말의 BET 비표면적은 18.0 ㎡/g이며, 염기도는 38.3 ㎛ol/㎡였다. 수증기 흡착량은, 수증기압 100 Pa에서 78 ml/g였다. 또한, 평균 입경은 1.1 ㎛, D90은 3.1 ㎛였다. 그 결과를 표 1에 나타낸다. The mixture was uniformly mixed with N-methylpyrrolidone in a nitrogen atmosphere, and then mixed with a jet mill (STJ-200 manufactured by Seishin Enterprise Co., Ltd., Japan) ) At a feed rate of 5 kg / h and a pressure of 0.7 MPa to obtain a calcium oxide powder whose particle surface was covered with an organic solvent. The calcium oxide powder thus obtained had a BET specific surface area of 18.0 m 2 / g and a basicity of 38.3 μmol / m 2. The amount of water vapor adsorption was 78 ml / g at a water vapor pressure of 100 Pa. The average particle diameter was 1.1 mu m and D90 was 3.1 mu m. The results are shown in Table 1.
[표 1][Table 1]
이상의 결과로부터, 실시예 1∼2의 산화칼슘은, 염기도가 25∼100 ㎛ol/㎡의 범위 내인 점에서 산성 가스의 흡착성이 우수하고, 또한 수증기압 100 Pa의 조건하에서의 수증기 흡착량이 200 ml/g 이상인 점에서 수분의 흡착성도 우수하다는 것을 알 수 있다. 한편, 비교예 1과 같이 진공 소성한 것은, 실시예 1∼2와 비교해서, BET 비표면적과 입경 분포가 크고, 염기도와 수증기 흡착량에서 떨어진다는 것을 알 수 있다. 또한, 비교예 2와 같이 분쇄 공정이 없는 것은, 수증기 흡착량이 떨어진다는 것을 알 수 있다. 또한, 비교예 3의 시판하는 건조제는 실시예 1∼3과 비교해서 입경이 크다는 것을 알 수 있다. 또한, 비교예 4와 같이 N-메틸피롤리돈으로 표면 처리한 것은 실시예 1∼3과 비교해서 수증기 흡착량에서 떨어진다는 것을 알 수 있다. From the above results, it can be seen that the calcium oxide of Examples 1 and 2 has an excellent adsorptivity of acid gas in that the basicity is within a range of 25 to 100 占 퐉 ol / m2 and the amount of adsorption of water vapor at a water vapor pressure of 100 Pa is 200 ml / , It can be seen that the adsorbability of water is also excellent. On the other hand, it can be seen that, in comparison with Examples 1 and 2, when the vacuum fired as in Comparative Example 1, the BET specific surface area and the particle size distribution are large, and the basicity and the amount of adsorption of water vapor are deteriorated. In addition, as in Comparative Example 2, the absence of the pulverization step indicates that the amount of water vapor adsorption is reduced. It is also understood that the commercially available desiccant of Comparative Example 3 has a larger particle size than those of Examples 1 to 3. It is also understood that the surface treated with N-methylpyrrolidone as in Comparative Example 4 is inferior in the amount of water vapor adsorption compared with Examples 1 to 3.
Claims (5)
상기 산화칼슘을 분말형으로 분쇄하는 분쇄 공정을 구비하는 것을 특징으로 하는 산화칼슘 분말의 제조 방법. A calcination step of calcining calcium hydroxide in the atmosphere under the conditions of 500 to 700 占 폚 to produce calcium oxide;
And a pulverizing step of pulverizing the calcium oxide into a powder form.
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