JP5300301B2 - Rotary dehumidification rotor - Google Patents
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- JP5300301B2 JP5300301B2 JP2008089606A JP2008089606A JP5300301B2 JP 5300301 B2 JP5300301 B2 JP 5300301B2 JP 2008089606 A JP2008089606 A JP 2008089606A JP 2008089606 A JP2008089606 A JP 2008089606A JP 5300301 B2 JP5300301 B2 JP 5300301B2
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- 238000007791 dehumidification Methods 0.000 title claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 179
- 239000000741 silica gel Substances 0.000 claims abstract description 98
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 98
- 239000011734 sodium Substances 0.000 claims abstract description 48
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 37
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 39
- 239000000017 hydrogel Substances 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- 239000004115 Sodium Silicate Substances 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 37
- 239000010953 base metal Substances 0.000 abstract description 36
- 150000003624 transition metals Chemical class 0.000 abstract description 27
- 239000011148 porous material Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 17
- 238000007654 immersion Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- -1 transition metal salt Chemical class 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 9
- 229910000358 iron sulfate Inorganic materials 0.000 description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 9
- 239000000499 gel Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Drying Of Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicon Compounds (AREA)
Abstract
Description
本発明は、耐水熱性に優れ、除湿剤として好適なシルカゲル及び回転式除湿ロータに関するものである。 The present invention relates to a silica gel and a rotary dehumidification rotor that are excellent in hydrothermal resistance and suitable as a dehumidifying agent.
従来より、シリカゲルやゼオライト等の吸湿剤を担持させたハニカム構造体が、除湿素子として広く使用されている。シリカゲルとゼオライトとを比較すると、一般的には相対湿度が低い場合にはゼオライトの方が吸湿量は多く、相対湿度が高い場合にはシリカゲルの方が吸湿量は多くなる。また、シリカゲルの中でも、Ａ形シリカゲルは相対湿度が低い場合の吸湿量は比較的多いものの、相対湿度が高くなるに従って吸湿量は頭打ちとなり、Ｂ形シリカゲルは概ね相対湿度９０％以下では、吸湿量が非常に低く、相対湿度９０％を越えるような高相対湿度の場合に非常に高い吸湿量を示す。 Conventionally, honeycomb structures carrying a hygroscopic agent such as silica gel or zeolite have been widely used as dehumidifying elements. When silica gel and zeolite are compared, in general, zeolite has a higher moisture absorption when the relative humidity is lower, and silica gel has a higher moisture absorption when the relative humidity is higher. Among silica gels, A type silica gel absorbs a relatively large amount of moisture when the relative humidity is low, but the amount of moisture absorption reaches a peak as the relative humidity increases. Is very low and exhibits a very high moisture absorption when the relative humidity exceeds 90%.
一方、特開２００１−９２３１号公報には、シリカゲルとしての酸化ケイ素９０．０〜９９．９質量部に対し、酸化鉄もしくは酸化鉄と他の金属酸化物との混合物０．１〜１０．０質量部が配合された除湿剤が開示されている。この除湿剤は湿度環境にかかわらず、高い吸湿性能を有する。 On the other hand, JP-A-2001-9231 discloses iron oxide or a mixture of iron oxide and another metal oxide in an amount of 0.1 to 10.0 with respect to 90.0 to 99.9 parts by mass of silicon oxide as silica gel. A dehumidifying agent in which parts by mass are blended is disclosed. This dehumidifying agent has high moisture absorption performance regardless of the humidity environment.
近年、被処理空気から露点−２０℃程度の乾燥空気を製造する回転式除湿ロータが知られている。回転式除湿ロータは、一般に除湿剤としてシリカゲルが担持されたハニカム状のロータ素子と、ロータ素子の端面を処理ゾーン、再生ゾーンに区画する固定プレートとからなるもので、ロータ素子は例えば１時間当たり数回〜５０回前後で回転し、処理ゾーンで素子の除湿剤（シリカゲル）が空気中の水分を吸着、再生ゾーンで７０℃以上の熱風で吸着した水分を脱着再生し、これを繰り返すことで空気中の水分を除湿する。このため、回転式除湿ロータで使用される除湿剤（シリカゲル）には、再生ゾーンでシリカゲル表面に水が吸着（存在）した状態で７０℃以上の熱に晒されることになり、長期間運転すると水と熱の影響でシリカゲルの性能が低下するという問題があった。このことから除湿剤の耐水熱性が要求される。
従って、本発明の目的は、耐水熱性に優れるシリカゲル及び回転式除湿ロータを提供することにある。 Accordingly, an object of the present invention is to provide a silica gel and a rotary dehumidification rotor that are excellent in hydrothermal resistance.
かかる実情において、本発明者らは鋭意検討を行った結果、遷移金属又は卑金属を含有し、ナトリウム含有量がＮａ２Ｏとして、０〜０．２質量％であるシリカゲル（除湿剤）が、耐水熱性に優れること等を見出し、本発明を完成するに至った。 In such a situation, as a result of intensive studies, the present inventors have found that silica gel (dehumidifier) containing transition metal or base metal and having a sodium content of 0 to 0.2% by mass as Na 2 O is water resistant. The inventors have found that it has excellent thermal properties and completed the present invention.
すなわち、本発明は、珪酸ナトリウム水溶液からなる液滴を乾燥して半固形状の液滴乾燥物を得るＩ工程、Ｉ工程で得られた液滴乾燥物をゲル化するII工程、II工程で得られたシリカヒドロゲル中に残存するナトリウムを洗浄除去するIII工程、洗浄されたシリカヒドロゲルを鉄塩又はアルミニウム塩を含む溶液に浸漬するIV工程、IV工程で得られた鉄又はアルミニウムドープシリカヒドロゲルを水洗するＶ工程を施すことにより製造されてなる、
鉄又はアルミニウムを含有し、ナトリウム含有量がＮａ ２ Ｏとして、０〜０．２質量％であるシリカゲルを担持したシリカゲル素子を備えることを特徴とする回転式除湿ロータを提供するものである。
That is , the present invention is a step I for drying a droplet made of an aqueous sodium silicate solution to obtain a semisolid droplet dried product, a step II for gelling the dried droplet obtained in step I, and a step II. Step III for washing and removing sodium remaining in the obtained silica hydrogel, Step IV for immersing the washed silica hydrogel in a solution containing an iron salt or an aluminum salt, Iron or aluminum doped silica hydrogel obtained in Step IV Manufactured by applying a V process of washing with water,
The present invention provides a rotary dehumidification rotor comprising a silica gel element supporting silica gel containing iron or aluminum and having a sodium content of 0 to 0.2% by mass as Na 2 O.
本発明のシリカゲルは、耐水熱性が顕著に優れ、その結果乾湿繰り返し耐久性も向上する。このため、１時間当たり数回〜数十回前後で回転し、除湿、再生及び冷却が繰り返される回転式除湿ロータの除湿剤としての使用に適する。 The silica gel of the present invention is remarkably excellent in hydrothermal resistance, and as a result, it is also improved in dry and wet repeated durability. For this reason, it is suitable for use as a dehumidifier of a rotary dehumidification rotor that rotates several times to several tens of times per hour and repeats dehumidification, regeneration, and cooling.
本発明のシリカゲルは、遷移金属又は卑金属を含有し、ナトリウム含有量がＮａ２Ｏとして、０〜０．２質量％である。遷移金属又は卑金属を含有し、ナトリウム含有量が０．２質量％を越えるものは、耐水熱性が低下し、結果として乾湿繰り返し耐久性も低下する。ナトリウム含有量０は測定限界値を言う。 Silica gel of the present invention contains a transition metal or a base metal, a sodium content is Na 2 O, which is 0 to 0.2 mass%. Those containing a transition metal or base metal and having a sodium content of more than 0.2% by mass have reduced hydrothermal resistance, resulting in reduced wet and dry repeated durability. A sodium content of 0 refers to a measurement limit value.
本発明のシリカゲルは、遷移金属又は卑金属がドープされたものである。遷移金属又は卑金属を導入することでシリカゲル中のナトリウム量が多くても耐水熱性が優れたものを得ることができる。また、遷移金属又は卑金属を導入することでシリカゲルの吸脱着特性が向上する。吸脱着特性とは吸着量が多く、脱着し易い特性を言う。なお、遷移金属又は卑金属を含まないシリカゲルは、ナトリウム含有量が測定限界以下でも耐水熱性が低下する。具体的には、本発明のシリカゲルは、シリカゲルとしての酸化珪素に対して、遷移金属又は卑金属の酸化物が配合されている。遷移金属又は卑金属の酸化物の配合量としては、概ね酸化珪素１００質量部中、０．１〜１０．０質量部である。 The silica gel of the present invention is doped with a transition metal or a base metal. By introducing a transition metal or a base metal, one having excellent hydrothermal resistance can be obtained even if the amount of sodium in the silica gel is large. Moreover, the adsorption / desorption characteristics of silica gel are improved by introducing a transition metal or a base metal. The adsorption / desorption characteristic means a characteristic that the adsorption amount is large and desorption is easy. In addition, the silica gel containing no transition metal or base metal has low hydrothermal resistance even when the sodium content is below the measurement limit. Specifically, in the silica gel of the present invention, a transition metal or base metal oxide is blended with silicon oxide as the silica gel. The compounding amount of the transition metal or base metal oxide is approximately 0.1 to 10.0 parts by mass in 100 parts by mass of silicon oxide.
遷移金属としては、鉄、チタン、ジルコニアが挙げられる。卑金属としてはアルミニウムが挙げられる。本発明のシリカゲルは、遷移金属がドープされたものが好ましく、特に鉄がドープされたものが吸脱着特性が高い点で好ましい。 Examples of the transition metal include iron, titanium, and zirconia. An example of the base metal is aluminum. The silica gel of the present invention is preferably doped with a transition metal, and particularly preferably doped with iron in view of high adsorption / desorption characteristics.
本発明のシリカゲルは、比表面積が５５０〜１０００ｍ２／ｇが好ましく、特に６５０〜９００ｍ２／ｇが好ましい。本発明のシリカゲルは、１０５℃×１００％、０．１２ＭＰａ、４８時間での耐水熱性試験における比表面積の低下率（劣化率）は２５％以下、特に２２％以下である。市販のシリカゲルの水蒸気劣化量は概ね３０〜７０％であり、本発明のシリカゲルの耐水熱性が高いことが判る。 The silica gel of the present invention preferably has a specific surface area of 550 to 1000 m 2 / g, particularly preferably 650 to 900 m 2 / g. The silica gel of the present invention has a specific surface area reduction rate (deterioration rate) of 25% or less, particularly 22% or less in a hydrothermal resistance test at 105 ° C. × 100%, 0.12 MPa, 48 hours. The amount of steam deterioration of commercially available silica gel is generally 30 to 70%, and it can be seen that the silica gel of the present invention has high hydrothermal resistance.
次に、本発明のシリカゲルの製造方法（第１の製造方法）を説明する。上記シリカゲルを製造するには、シリカゲルを洗浄して、シリカゲル中のナトリウム分を低減する工程と、原料のシリカゲルに遷移金属又は卑金属を導入する工程とを行えばよい。 Next, the manufacturing method (1st manufacturing method) of the silica gel of this invention is demonstrated. In order to produce the silica gel, the step of washing the silica gel to reduce the sodium content in the silica gel and the step of introducing a transition metal or base metal into the raw silica gel may be performed.
原料のシリカゲルとしては、Ａ型シリカゲル、Ｂ型シリカゲルあるいはそれ以外の公知のシリカゲルが挙げられる。これらのシリカゲルは市販のものが使用できる。 Examples of the raw silica gel include A-type silica gel, B-type silica gel, and other known silica gels. Commercially available silica gels can be used.
シリカゲルを洗浄して、シリカゲル中のナトリウム分を低減する工程は、シリカゲル中に残存するナトリウムを、シリカゲル中、例えば０．２％質量以下となるまで洗浄除去する工程である。洗浄は酸洗浄および水洗浄を行なうことが、酸洗浄でシリカゲル中に残存するナトリウム分を、水洗浄でゲル内の硫酸ナトリウム及び過剰な酸を確実に除去できる点で好ましい。酸洗浄は、例えば被洗浄物のシリカゲルをｐＨ０．２の硫酸水溶液中に室温で、１０分程度浸漬し、これを数回行えばよい。 The step of washing the silica gel to reduce the sodium content in the silica gel is a step of washing and removing sodium remaining in the silica gel in the silica gel until, for example, 0.2% by mass or less. Washing is preferably carried out by acid washing and water washing because the sodium content remaining in the silica gel by acid washing can be surely removed from the sodium sulfate and excess acid in the gel by water washing. The acid cleaning may be performed, for example, by immersing the silica gel to be cleaned in a sulfuric acid aqueous solution having a pH of 0.2 at room temperature for about 10 minutes and performing this several times.
第１の製造方法において、原料のシリカゲル中に０．２質量％を越える量のナトリウムが含有されている場合には、酸による洗浄を行い、ナトリウムを低減させる。この時、ナトリウム含有量は０．２質量％以下にすることが望ましいが、ナトリウム含有量が０．２質量％を越える量であっても、その後の遷移金属又は卑金属を導入する工程で残存ナトリウム分を除去して、ナトリウム含有量を０．２質量％以下としてもよい。 In the first production method, when the starting silica gel contains sodium in an amount exceeding 0.2% by mass, washing with an acid is performed to reduce sodium. At this time, it is desirable that the sodium content is 0.2% by mass or less, but even if the sodium content exceeds 0.2% by mass, the residual sodium is not removed in the subsequent transition metal or base metal introduction step. The sodium content may be 0.2% by mass or less by removing the portion.
シリカゲルに遷移金属又は卑金属を導入する工程は、ナトリウム量が低減されたシリカゲルを、遷移金属塩又は卑金属塩を含む溶液に浸漬する工程である。遷移金属又は卑金属をシリカゲルに導入することで、残存ナトリウム分を除去すると共に、吸脱着特性を高めることができる。また、残存ナトリウム分が少なくなるため、耐水熱性が向上する。 The step of introducing the transition metal or base metal into the silica gel is a step of immersing the silica gel in which the amount of sodium is reduced in a solution containing the transition metal salt or the base metal salt. By introducing the transition metal or base metal into the silica gel, the residual sodium content can be removed and the adsorption / desorption characteristics can be enhanced. Further, since the residual sodium content is reduced, the hydrothermal resistance is improved.
遷移金属としては、前記シリカゲルの遷移金属と同様のものが挙げられる。また、遷移金属塩は、硫酸の遷移金属塩が好ましく、特に硫酸鉄が好ましい。卑金属としては、前記シリカゲルの卑金属と同様のものが挙げられる。また、卑金属塩は、硫酸の卑金属塩が好ましく、特に硫酸アルミニウムが好ましい。また、遷移金属塩又は卑金属塩はそれぞれ１種又は２種の組み合わせであってもよい。また、遷移金属塩と卑金属塩を組み合わせて使用してもよい。 Examples of the transition metal include those similar to the transition metal of the silica gel. The transition metal salt is preferably a transition metal salt of sulfuric acid, and particularly preferably iron sulfate. Examples of the base metal include those similar to the base metal of the silica gel. The base metal salt is preferably a base metal salt of sulfuric acid, particularly preferably aluminum sulfate. Moreover, 1 type or 2 types of combinations may be sufficient as a transition metal salt or a base metal salt, respectively. Moreover, you may use combining a transition metal salt and a base metal salt.
遷移金属塩として硫酸鉄を使用した場合の浸漬条件としては、硫酸鉄５〜２０％溶液、浸漬温度３０〜６０℃、浸漬時間５〜６０分、ｐＨは成り行きである。卑金属塩として硫酸アルミニウムを使用した場合の浸漬条件としては、硫酸アルミニウム５〜２０％溶液、浸漬温度３０〜６０℃、浸漬時間５〜６０分、ｐＨは成り行きである。上記の浸漬条件であれば、シリカゲルとしての酸化珪素１００質量部中、遷移金属又は卑金属の酸化物０．１〜１０質量部を導入することができる。 As the immersion conditions when iron sulfate is used as the transition metal salt, the iron sulfate 5 to 20% solution, the immersion temperature 30 to 60 ° C., the immersion time 5 to 60 minutes, and the pH are appropriate. As the immersion conditions when aluminum sulfate is used as the base metal salt, the aluminum sulfate 5 to 20% solution, the immersion temperature 30 to 60 ° C., the immersion time 5 to 60 minutes, and the pH are appropriate. If it is said immersion conditions, 0.1-10 mass parts of transition metal or base metal oxides can be introduce | transduced in 100 mass parts of silicon oxides as a silica gel.
本発明のシリカゲルは、上記第１の製造方法以外の方法（第２の製造方法）で製造することができる。すなわち、第２の製造方法は、珪酸ナトリウム水溶液からなる液滴を乾燥して半固形状の液滴乾燥物を得るＩ工程、Ｉ工程で得られた液滴乾燥物をゲル化するＩＩ工程、ＩＩ工程で得られたシリカヒドロゲル中に残存するナトリウムを洗浄除去するＩＩＩ工程、洗浄されたシリカヒドロゲルを遷移金属塩又は卑金属塩を含む溶液に浸漬するＩＶ工程、ＩＶ工程で得られた遷移金属又は卑金属ドープシリカヒドロゲルを水洗するＶ工程を有する。 The silica gel of the present invention can be produced by a method other than the first production method (second production method). That is, the second production method is a step I for drying a droplet made of a sodium silicate aqueous solution to obtain a semi-solid droplet dried product, a step II for gelling the droplet dried product obtained in the step I, Step III for washing away sodium remaining in the silica hydrogel obtained in Step II, Step IV for immersing the washed silica hydrogel in a solution containing a transition metal salt or a base metal salt, Transition metal obtained in Step IV or It has V process of washing a base metal dope silica hydrogel with water.
Ｉ工程は、珪酸ナトリウム水溶液からなる液滴を、好ましくは保水率５０〜１５０％、特に好ましくは７０〜１２０％となるように乾燥して半固形状の液滴乾燥物を得る工程である。なお、保水率１００％は珪酸ナトリウムの質量と水の質量が同じであることを意味する。珪酸ナトリウム水溶液は従来のシリカゲルの合成において使用されるものが、同様に使用できる。 Step I is a step of drying a droplet made of an aqueous sodium silicate solution so that the water retention rate is preferably 50 to 150%, particularly preferably 70 to 120% to obtain a semisolid droplet dried product. In addition, 100% of water retention means that the mass of sodium silicate and the mass of water are the same. The sodium silicate aqueous solution used in the synthesis of conventional silica gel can be used in the same manner.
液滴乾燥物は、フッソ樹脂シートなどの撥水性シート上に珪酸ナトリウム水溶液を滴下することで得られる。乾燥条件は、液滴の保水率が上記の範囲となるような条件であり、具体的には、７０〜１１０℃の乾燥機中、１〜５分である。液滴乾燥物の保水率が上記範囲であれば、相対的に表層部の保水率が低く、内部の保水率が高い半固体又は固体に近いものとすることができ、これをゲル化させることで、相対的に表層部の細孔径が小さく、中心部の細孔径が大きいシリカゲルが得られ、これにより相対湿度が高い場合と低い場合の双方の場合の吸湿量が共に優れたものとなる。 A dried droplet is obtained by dropping a sodium silicate aqueous solution onto a water repellent sheet such as a fluorine resin sheet. The drying conditions are such that the water retention rate of the droplets falls within the above range, and specifically, 1 to 5 minutes in a dryer at 70 to 110 ° C. If the water retention rate of the dried droplets is in the above range, the water retention rate of the surface layer portion is relatively low, and the internal water retention rate can be semi-solid or close to a solid, which can be gelled. Thus, a silica gel having a relatively small pore diameter in the surface layer portion and a large pore diameter in the central portion is obtained, whereby the moisture absorption amount in both cases where the relative humidity is high and low is excellent.
半固形状の液滴乾燥物中の水分量は、乾燥前後の重量測定結果から求めることができる。半固形状の液滴乾燥物は、最大長さが０．５〜１０ｍｍ程度であり、最大長さが小さ過ぎると、求める細孔分布が得られない点で好ましくなく、直径が大き過ぎると、内部までゲル化させることができない点で好ましくない。半固形状の液滴乾燥物の最大長さは、液滴乾燥物を上から見た場合の（平面視）最大長さを言う。 The amount of water in the semi-solid droplet dried product can be determined from the results of weight measurement before and after drying. The semi-solid droplet dried product has a maximum length of about 0.5 to 10 mm, and if the maximum length is too small, it is not preferable in that the desired pore distribution cannot be obtained, and if the diameter is too large, It is not preferable in that it cannot be gelled to the inside. The maximum length of the semi-solid droplet dried product refers to the maximum length when the droplet dried product is viewed from above (plan view).
半固形状とは流動性がない状態を言い、撥水性シートを傾斜させても流れ出すことがない。また、液滴乾燥物は撥水性シートに付着しているため、ゲル化液中へ撥水性シートごと浸漬すればよく、浸漬方法も容易である。このように、ゲル化させる前の珪酸ナトリウム原料を溶液として使用しない点で従来の合成法とは大きく相違する。 The semi-solid state means a state having no fluidity and does not flow out even when the water repellent sheet is inclined. Moreover, since the dried droplets are attached to the water-repellent sheet, it is only necessary to immerse the water-repellent sheet together in the gelling solution, and the dipping method is easy. Thus, it is greatly different from the conventional synthesis method in that the sodium silicate raw material before gelation is not used as a solution.
ＩＩ工程はＩ工程で得られた液滴乾燥物をゲル化する工程である。すなわち、ＩＩ工程は、液滴乾燥物を酸水溶液に浸漬することで珪酸ナトリウムから脱ナトリウムし、シリカヒドロゲルとする工程である。酸水溶液としては、硫酸水溶液又は塩酸水溶液が挙げられ、ｐＨは０．５〜１．８、好適には０．８〜１．３である。酸水溶液には硫酸アンモニウム等のｐＨ調整剤が含まれていてもよい。 Step II is a step of gelling the dried droplets obtained in Step I. That is, the step II is a step of removing sodium from sodium silicate by immersing the dried droplet in an acid aqueous solution to form a silica hydrogel. Examples of the acid aqueous solution include an aqueous sulfuric acid solution and an aqueous hydrochloric acid solution, and the pH is 0.5 to 1.8, preferably 0.8 to 1.3. The acid aqueous solution may contain a pH adjusting agent such as ammonium sulfate.
酸水溶液として硫酸−アンモニア溶液を使用した場合の好適な浸漬条件は、ｐＨ０．５〜１．８において浸漬温度が２０〜４５℃、１５分以上、特にｐＨ０．７〜１．５において浸漬温度が２５〜４３℃、１５〜５０分、更にｐＨ０．８〜１．３において浸漬温度が３０〜４２℃、１５〜５０分である。上記範囲内であれば、最終的に得られるシリカゲルの比表面積が５５０ｍ２／ｇ以上のものとなる点で好ましい。 The preferred soaking conditions when using a sulfuric acid-ammonia solution as the aqueous acid solution are as follows: the soaking temperature is 20 to 45 ° C. for 15 minutes or more at a pH of 0.5 to 1.8, and the soaking temperature is particularly preferably at a pH of 0.7 to 1.5. The immersion temperature is 30 to 42 ° C. and 15 to 50 minutes at 25 to 43 ° C. and 15 to 50 minutes, and further at pH 0.8 to 1.3. If it is in the said range, it is preferable at the point from which the specific surface area of the silica gel finally obtained becomes a thing of 550 m < 2 > / g or more.
ＩＩ工程は、上記のゲル化処理により、１０ｎｍ以上の大きな細孔が多く存在するシリカヒドロゲルを得ることができる。このような大きな細孔を含むシリカヒドロゲルが形成される理由は、ｐＨ値が高い珪酸ナトリウムの液滴乾燥物の表面からｐＨ０．５〜１．８の酸水溶液が内部に浸透し、表面から脱ナトリウムしてゲル化が進行するという特有のゲル化作用によるものと思われる。ＩＩ工程で得られるシリカヒドロゲルの細孔分布は、細孔径が２〜５０ｎｍ、平均細孔直径７〜９ｎｍ、比表面積が１００〜１５０ｍ２/ｇのブロードな細孔分布を有する。 In step II, a silica hydrogel having many large pores of 10 nm or more can be obtained by the gelation treatment described above. The reason why such a silica hydrogel having large pores is formed is that an acid aqueous solution having a pH of 0.5 to 1.8 penetrates from the surface of a sodium silicate droplet dried product having a high pH value, and is removed from the surface. It seems to be due to the unique gelling action of gelation due to sodium. The pore distribution of the silica hydrogel obtained in step II has a broad pore distribution with a pore diameter of 2 to 50 nm, an average pore diameter of 7 to 9 nm, and a specific surface area of 100 to 150 m 2 / g.
ＩＩＩ工程は、ＩＩ工程で得られたシリカヒドロゲル中に残存するナトリウムを洗浄除去する工程である。洗浄は酸洗浄および水洗浄の２工程を行なうことが、前工程でシリカヒドロゲル中に残存するナトリウム分を、後工程でゲル内の硫酸ナトリウム及び過剰な酸を確実に除去できる点で好ましい。酸洗浄は、ｐＨ０．７〜０．８の硫酸水溶液を、１５〜２５℃の温度下、１０分程度行うことが好適である。ＩＩＩ工程で得られるシリカヒドロゲルの細孔分布は、細孔径が２〜５０ｎｍ、平均細孔直径３．５〜７ｎｍ、比表面積が２００〜４５０ｍ２/ｇのブロードな細孔分布を有する。ＩＩＩ工程で得られるシリカヒドロゲルの平均細孔直径は、ＩＩ工程で得られるシリカヒドロゲルよりも小さく、比表面積は大きくなる。 Step III is a step of washing away sodium remaining in the silica hydrogel obtained in Step II. Washing is preferably performed in two steps, acid washing and water washing, from the viewpoint that the sodium content remaining in the silica hydrogel in the previous step and sodium sulfate and excess acid in the gel can be reliably removed in the subsequent step. The acid cleaning is preferably performed with a sulfuric acid aqueous solution having a pH of 0.7 to 0.8 at a temperature of 15 to 25 ° C. for about 10 minutes. The pore distribution of the silica hydrogel obtained in step III has a broad pore distribution with a pore diameter of 2 to 50 nm, an average pore diameter of 3.5 to 7 nm, and a specific surface area of 200 to 450 m 2 / g. The average pore diameter of the silica hydrogel obtained in Step III is smaller than that of the silica hydrogel obtained in Step II, and the specific surface area is increased.
ＩＶ工程は、ＩＩＩ工程で得られた洗浄シリカヒドロゲルを、遷移金属塩又は卑金属塩を含む溶液に浸漬する工程である。遷移金属又は卑金属をシリカゲルヒドロゲルに導入することで、残存ナトリウム分を除去すると共に、吸脱着性能を高めることができる。また、シリカゲル中のナトリウム量が多くても耐水熱性が高いものを得ることができる。 Step IV is a step of immersing the washed silica hydrogel obtained in Step III in a solution containing a transition metal salt or a base metal salt. By introducing the transition metal or base metal into the silica gel hydrogel, the residual sodium content can be removed and the adsorption / desorption performance can be enhanced. Moreover, even if there is much sodium amount in a silica gel, what has high hydrothermal resistance can be obtained.
遷移金属及び卑金属としては、前記シリカゲルの遷移金属及び卑金属と同様のものが挙げられる。また、遷移金属塩及び卑金属塩は、硫酸の遷移金属塩又は卑金属塩が好ましく、特に硫酸鉄や硫酸アルミニウムが好ましい。また、これらの金属塩は１種又は２種の組み合わせであってもよい。これらの金属塩として硫酸鉄、硫酸アルミニウムを使用した場合の浸漬条件は、前記第１の製造方法における金属塩として硫酸鉄、硫酸アルミニウムを使用した場合の浸漬条件と同様である。 As a transition metal and a base metal, the same thing as the transition metal and base metal of the said silica gel is mentioned. Moreover, the transition metal salt and the base metal salt are preferably a transition metal salt or a base metal salt of sulfuric acid, particularly preferably iron sulfate or aluminum sulfate. These metal salts may be one kind or a combination of two kinds. The immersion conditions when iron sulfate and aluminum sulfate are used as these metal salts are the same as the immersion conditions when iron sulfate and aluminum sulfate are used as the metal salts in the first production method.
Ｖ工程は、ＩＶ工程で得られた遷移金属又は卑金属ドープシリカヒドロゲルを水洗し、余剰の遷移金属等を除去する工程である。この工程により、遷移金属又は卑金属ドープシリカヒドロゲル内に残存する余分な塩が除去される。水洗工程後のシリカヒドロゲルは、公知の乾燥条件により乾燥され、本発明のシリカゲルとなる。 V process is a process of washing the transition metal or base metal doped silica hydrogel obtained in the IV process with water to remove excess transition metal and the like. This step removes excess salt remaining in the transition metal or base metal doped silica hydrogel. The silica hydrogel after the water washing step is dried under a known drying condition to form the silica gel of the present invention.
第２の製造方法のＩＩＩ工程において、ナトリウム含有量は０．２質量％以下にすることが望ましいが、ナトリウム含有量が０．２質量％を越える量であっても、その後のＩＶ工程の遷移金属又は卑金属を導入する工程で残存ナトリウム分を除去して、ナトリウム含有量を０．２質量％以下としてもよい。 In step III of the second production method, the sodium content is desirably 0.2% by mass or less, but even if the sodium content exceeds 0.2% by mass, the transition of the subsequent IV step Residual sodium content may be removed in the step of introducing a metal or base metal, and the sodium content may be 0.2% by mass or less.
シリカゲルの第２の製造方法によれば、シリカゲル中の残存ナトリウム分が特定値以下となるため耐水熱性が向上し、その結果乾湿繰り返し耐久性が向上する。また、ｐＨの高い珪酸ナトリウムの液滴乾燥物をｐＨの低い酸溶液に浸漬してシリカヒドロゲルを得るため、シリカヒドロゲル内部に大きな細孔を形成できる。そして、内部に大きな細孔を有するシリカヒドロゲルに遷移金属又は卑金属をドープするため、大きな細孔を内部に有したまま、表面部に小さな細孔を形成できる。このため、当該方法で得られたシリカゲル又はその粉砕物は、従来にないユニークな細孔構造を有するため、低湿度及び高湿度での吸湿量が共に顕著に高いものとなる。 According to the second method for producing silica gel, the residual sodium content in the silica gel is not more than a specific value, so that the hydrothermal resistance is improved, and as a result, the wet and dry repeated durability is improved. Moreover, since the silica hydrogel is obtained by immersing the dried solution of sodium silicate having a high pH in an acid solution having a low pH, large pores can be formed inside the silica hydrogel. And since a transition metal or a base metal is doped to the silica hydrogel which has a large pore inside, a small pore can be formed in a surface part, having a large pore inside. For this reason, the silica gel obtained by the method or the pulverized product thereof has an unprecedented unique pore structure, so that the moisture absorption at low and high humidity is remarkably high.
本発明の回転式除湿ロータは、本発明のシリカゲルを担持したシリカゲル素子を備えるものである。回転式除湿ロータは、本発明のシリカゲルが除湿剤として繊維質担体に担持されたハニカム状のロータ素子と、ロータ素子の端面を少なくとも除湿ゾーンと再生ゾーン、好適には、除湿ゾーン、再生ゾーン及び冷却ゾーンに区画する固定プレートとからなる。本発明の回転式除湿ロータは、シリカゲル以外は公知の構造のものが適用でき、ロータ素子を回転駆動する駆動手段と、被処理空気を除湿ゾーンに通過させて乾燥空気を供給する供給経路と、再生空気を冷却ゾーンに通過させた後、加熱して該再生ゾーンに通過させる排気経路などを備えたものである。 The rotary dehumidifying rotor of the present invention includes a silica gel element carrying the silica gel of the present invention. A rotary dehumidification rotor includes a honeycomb-shaped rotor element in which the silica gel of the present invention is supported on a fibrous carrier as a dehumidifying agent, and at least a dehumidification zone and a regeneration zone, preferably a dehumidification zone, a regeneration zone, and an end face of the rotor element. It consists of a fixed plate that partitions into a cooling zone. The rotary dehumidification rotor of the present invention can be of a known structure other than silica gel, a driving means for rotationally driving the rotor element, a supply path for supplying the dry air by passing the air to be treated through the dehumidification zone, After the regeneration air is passed through the cooling zone, it is provided with an exhaust passage that is heated and passed through the regeneration zone.
本発明の回転式除湿ロータにおいて、除湿剤として使用するシリカゲル粉末の平均粒径は１．０〜１０μｍ、好ましくは２〜８μｍである。該シリカゲル粉末の平均粒径が、小さ過ぎると、繊維質担体である繊維間空隙に対する該シリカゲル粉末の大きさが、小さくなり過ぎるため、該シリカゲル粉末が、該繊維間空隙から抜け易くなり、繊維質担体から脱落し易くなり、また、該シリカゲル粉末の平均粒径が大き過ぎると、該シリカゲル粉末が大き過ぎるので、シリカゲル内部への水分の拡散速度が低くなるため、又は繊維質担体との接着面積が多くなり過ぎるため、吸湿性能が低くなり易い。 In the rotary dehumidification rotor of the present invention, the average particle size of the silica gel powder used as the dehumidifying agent is 1.0 to 10 μm, preferably 2 to 8 μm. If the average particle size of the silica gel powder is too small, the size of the silica gel powder with respect to the inter-fiber gap that is the fibrous carrier becomes too small, so that the silica gel powder is easily removed from the inter-fiber gap. If the average particle size of the silica gel powder is too large, the silica gel powder is too large, and therefore, the diffusion rate of moisture into the silica gel becomes low, or the adhesion to the fibrous carrier. Since the area becomes too large, the moisture absorption performance tends to be low.
本発明の回転式除湿ロータにおいて、ロータ素子は例えば１時間当たり数回〜５０回前後で回転し、処理ゾーンで素子のシリカゲルが空気中の水分を吸着、再生ゾーンで７０℃以上の熱風で吸着した水分を脱着再生し、これを繰り返すことで空気中の水分を除湿する。このため、再生ゾーンでシリカゲル表面に水が吸着（存在）した状態で７０℃以上の熱に晒され、且つ長期間運転しても、除湿剤の性能が低下することがなく、除湿剤の交換頻度が低減でき好都合である。また、第２の製造方法で製造されたシリカゲルは、低湿度及び高湿度での吸湿量が共に顕著に高いため、回転式除湿ロータに好適である。 In the rotary dehumidification rotor of the present invention, the rotor element rotates, for example, several times to around 50 times per hour, the silica gel of the element adsorbs moisture in the air in the processing zone, and adsorbs with hot air of 70 ° C. or more in the regeneration zone. The moisture in the air is desorbed and regenerated, and this is repeated to dehumidify the moisture in the air. For this reason, it is possible to replace the dehumidifier without degrading the performance of the dehumidifier even if it is exposed to heat of 70 ° C or higher with water adsorbed (existing) on the silica gel surface in the regeneration zone and operated for a long time. It is convenient because the frequency can be reduced. Further, the silica gel produced by the second production method is suitable for a rotary dehumidification rotor because the moisture absorption amount at both low and high humidity is remarkably high.
次に、実施例を挙げて本発明を更に具体的に説明するが、これは単に例示であって、本発明を制限するものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.
（シリカゲルの合成）
ＳｉＯ２/Ｎａ２Ｏ（モル比）＝３の珪酸ナトリウム（ＪＩＳ ３号）水溶液を、フッ素樹脂のシート上に、ノズルから３０μＬづつ滴下して、多数の液滴を形成した。液滴は適宜の間隔で形成した。次いで、１１０℃の乾燥機中、２分間保持して保水率１００％の半固形状の液滴乾燥物を得た（Ｉ工程）。
(Synthesis of silica gel)
An aqueous solution of sodium silicate (JIS No. 3) having a SiO 2 / Na 2 O (molar ratio) = 3 was dropped from a nozzle on a fluororesin sheet by 30 μL to form a large number of droplets. Droplets were formed at appropriate intervals. Subsequently, it was kept in a dryer at 110 ° C. for 2 minutes to obtain a semisolid droplet dried product having a water retention rate of 100% (Step I).
Ｉ工程で得られたフッ素樹脂シート上の液滴乾燥物を、フッ素樹脂シートから分離し、ｐＨ１の１０％硫酸−アンモニア溶液中に３５℃、６０分間浸漬した（ＩＩ工程）。ＩＩ工程により、液滴乾燥物の珪酸ソーダは脱ナトリウムされ、シリカヒドロゲルとなった。 The dried droplets on the fluororesin sheet obtained in the step I were separated from the fluororesin sheet and immersed in a 10% sulfuric acid-ammonia solution having a pH of 1 at 35 ° C. for 60 minutes (step II). By the step II, sodium silicate as a dried droplet was sodium-free to form a silica hydrogel.
次いで、ＩＩ工程で得られたシリカヒドロゲルを、２％硫酸溶液中に２０℃、１０分浸漬し酸洗浄した。次いで、酸洗浄済みのシリカヒドロゲルをさらに水洗した（ＩＩＩ工程）。水洗条件は、シリカヒドロゲルを水に２０℃、１０分浸漬した。 Next, the silica hydrogel obtained in the step II was immersed in a 2% sulfuric acid solution at 20 ° C. for 10 minutes and washed with acid. Next, the acid-washed silica hydrogel was further washed with water (step III). Washing conditions were that silica hydrogel was immersed in water at 20 ° C. for 10 minutes.
次いで、ＩＩＩ工程で得られた洗浄シリカヒドロゲルをｐＨ１．２の１０％硫酸鉄溶液に３５℃、３０分浸漬した（ＩＶ工程）。また、得られた硫酸鉄処理シリカヒドロゲルは、更に水洗した（Ｖ工程）。その後、１１０℃、３時間乾燥処理を行い鉄を含有したシリカゲルＡを得た。 Next, the washed silica hydrogel obtained in Step III was immersed in a 10% iron sulfate solution having a pH of 1.2 at 35 ° C. for 30 minutes (Step IV). Moreover, the obtained iron sulfate-treated silica hydrogel was further washed with water (Step V). Thereafter, drying treatment was performed at 110 ° C. for 3 hours to obtain silica gel A containing iron.
実施例１においては、酸浸漬と水洗を数回繰り返すことにより、シリカゲル中のＮａ２Ｏ含有量を０．１６質量％とした。鉄を含有したシリカゲルＡについて、下記の耐水熱性評価試験を行った。その結果、耐水熱性評価試験前後のシリカゲル比表面積の低下率は２３％であった（表１参照）。 In Example 1, the content of Na 2 O in the silica gel was set to 0.16% by mass by repeating acid dipping and water washing several times. The following hydrothermal resistance evaluation test was performed on silica gel A containing iron. As a result, the rate of decrease in the specific surface area of the silica gel before and after the hydrothermal resistance evaluation test was 23% (see Table 1).
（耐水熱性評価試験）
シリカゲルを１０５℃×１００％、０．１２ＭＰａの水蒸気雰囲気下に４８時間晒し、水蒸気処理前後の比表面積を測定し、水蒸気処理後の比表面積の低下率を測定することで評価した。すなわち、比表面積の低下率（％）＝（（水蒸気処理前の比表面積ｍ２／ｇ）−（水蒸気処理後の比表面積ｍ２／ｇ））×１００／（水蒸気処理前の比表面積ｍ２／ｇ）で求めた。
(Hydrothermal resistance evaluation test)
The silica gel was exposed to a steam atmosphere of 105 ° C. × 100% and 0.12 MPa for 48 hours, the specific surface area before and after the steam treatment was measured, and the reduction rate of the specific surface area after the steam treatment was measured. That is, the rate of decrease in specific surface area (%) = ((specific surface area m 2 / g before water vapor treatment) − (specific surface area m 2 / g after water vapor treatment)) × 100 / (specific surface area m 2 before water vapor treatment) / G).
実施例１のＩＩ工程における１０％硫酸−アンモニア溶液中に３５℃、６０分間の浸漬条件に代えて、１０％硫酸−アンモニア溶液中に３５℃、９０分間の浸漬条件とした以外は、実施例１と同様の方法で鉄を含有したシリカゲルＢを合成した。 Example 1 except that the immersion conditions were 35 ° C. and 60 minutes in a 10% sulfuric acid-ammonia solution instead of the immersion conditions at 35 ° C. and 60 minutes in the 10% sulfuric acid-ammonia solution in Step II of Example 1. In the same manner as in No. 1, silica gel B containing iron was synthesized.
得られたシリカゲルＢのＮａ２Ｏ含有量は０質量％（未検出）であった。同様に耐水熱性評価試験を行った結果、その耐水熱性評価試験前後のシリカゲル比表面積の低下率は２６％であった（表１参照）。 The obtained silica gel B had a Na 2 O content of 0% by mass (not detected). Similarly, as a result of the hydrothermal resistance evaluation test, the decrease rate of the specific surface area of the silica gel before and after the hydrothermal resistance evaluation test was 26% (see Table 1).
ＩＶ工程における１０％硫酸鉄溶液に代えて、１０％硫酸アルミニウム溶液とした以外は、実施例１と同様の方法でアルミニウムを含有したシリカゲルＣを合成した。 Silica gel C containing aluminum was synthesized in the same manner as in Example 1 except that a 10% aluminum sulfate solution was used instead of the 10% iron sulfate solution in step IV.
得られたシリカゲルＣのＮａ２Ｏ含有量は０．０６質量％であった。同様に耐水熱性評価試験を行った結果、その耐水熱性評価試験前後のシリカゲル比表面積の低下率は２５％であった（表１参照）。
比較例１
The obtained silica gel C had a Na 2 O content of 0.06% by mass. Similarly, as a result of the hydrothermal resistance evaluation test, the decrease rate of the specific surface area of the silica gel before and after the hydrothermal resistance evaluation test was 25% (see Table 1).
Comparative Example 1
実施例１のＩＩ工程における１０％硫酸−アンモニア溶液中に３５℃、６０分間の浸漬条件に代えて、１０％硫酸−アンモニア溶液中に３５℃、３０分間の浸漬条件としたこと、実施例１のＩＩＩ工程における酸洗浄と水洗浄に代えて、水洗浄のみとしたこと以外は、実施例１と同様の方法で鉄を含有したシリカゲルＤを合成した。 In place of the immersion condition of 35 ° C. for 60 minutes in the 10% sulfuric acid-ammonia solution in Step II of Example 1, the immersion condition of 35 ° C. for 30 minutes in the 10% sulfuric acid-ammonia solution was used. Silica gel D containing iron was synthesized in the same manner as in Example 1 except that only water washing was used instead of acid washing and water washing in Step III.
得られたシリカゲルＤのＮａ２Ｏ含有量は１．６質量％であった。同様に耐水熱性評価試験を行った結果、その耐水熱性評価試験前後のシリカゲル比表面積の低下率は４４％であった（表１参照）。
比較例２
The obtained silica gel D had a Na 2 O content of 1.6% by mass. Similarly, as a result of the hydrothermal resistance evaluation test, the decrease rate of the silica gel specific surface area before and after the hydrothermal resistance evaluation test was 44% (see Table 1).
Comparative Example 2
実施例１のＩＩ工程における１０％硫酸−アンモニア溶液中に３５℃、６０分間の浸漬条件に代えて、１０％硫酸−アンモニア溶液中に３５℃、５０分間の浸漬条件としたこと、実施例１のＩＩＩ工程における酸洗浄と水洗浄に代えて、水洗浄のみとしたこと以外は、実施例１と同様の方法で鉄を含有したシリカゲルＥを合成した。 In place of the immersion condition of 35 ° C. for 60 minutes in the 10% sulfuric acid-ammonia solution in Step II of Example 1, the immersion condition of 35 ° C. for 50 minutes was set in the 10% sulfuric acid-ammonia solution. Silica gel E containing iron was synthesized in the same manner as in Example 1 except that only water washing was used instead of acid washing and water washing in Step III.
得られたシリカゲルＥのナトリウム含有量は０．６質量％であった。同様に耐水熱性評価試験を行った結果、その耐水熱性評価試験前後のシリカゲル比表面積の低下率は３０％であった（表１参照）。
比較例３
The sodium content of the obtained silica gel E was 0.6% by mass. Similarly, as a result of the hydrothermal resistance evaluation test, the decrease rate of the specific surface area of the silica gel before and after the hydrothermal resistance evaluation test was 30% (see Table 1).
Comparative Example 3
実施例１のＩＩ工程における１０％硫酸−アンモニア溶液中に３５℃、６０分間の浸漬まで実施した後、実施例１のＩＩＩ及びＩＶ工を実施せず、水洗を行い、鉄を含有しにないシリカゲルＦを合成した。 After carrying out until immersion for 60 minutes in 35% of the sulfuric acid-ammonia solution in the II step of Example 1, the III and IV processes of Example 1 are not carried out, and the water is washed and does not contain iron. Silica gel F was synthesized.
得られたシリカゲルＦのＮａ２Ｏ含有量は０．９質量％であった。同様に耐水熱性評価試験を行った結果、その耐水熱性評価試験前後のシリカゲル比表面積の低下率は３３％であった（表１参照）。 The obtained silica gel F had a Na 2 O content of 0.9% by mass. Similarly, as a result of the hydrothermal resistance evaluation test, the decrease rate of the specific surface area of the silica gel before and after the hydrothermal resistance evaluation test was 33% (see Table 1).
表１の結果から、実施例であるシリカゲルＡ〜Ｃは、耐水熱性評価試験に優れる。一方、比較例であるシリカゲルＤ〜Ｆは、耐水熱性評価試験に劣る。このため、シリカゲルＡ〜Ｃを除湿剤とした担持したロータ素子を備える回転式除湿ロータの場合、長期間運転しても、除湿剤の性能が低下することがなく、除湿剤の交換頻度が低減できる。 From the results of Table 1, silica gels A to C as examples are excellent in hydrothermal resistance evaluation tests. On the other hand, silica gels D to F which are comparative examples are inferior to the hydrothermal resistance evaluation test. For this reason, in the case of a rotary dehumidification rotor equipped with a supported rotor element using silica gels A to C as a dehumidifying agent, the performance of the dehumidifying agent does not deteriorate even when operated for a long period of time, and the replacement frequency of the dehumidifying agent is reduced. it can.
Claims (1)
鉄又はアルミニウムを含有し、ナトリウム含有量がＮａ ２ Ｏとして、０〜０．２質量％であるシリカゲルを担持したシリカゲル素子を備えることを特徴とする回転式除湿ロータ。 In the silica hydrogel obtained in Step I, Step II of gelling the droplet dried material obtained in Step I, drying the droplet made of an aqueous solution of sodium silicate to obtain a semisolid droplet dried material Step III for washing and removing residual sodium, Step IV for immersing the washed silica hydrogel in a solution containing an iron salt or aluminum salt, Step V for washing the iron or aluminum-doped silica hydrogel obtained in Step IV with water Manufactured by
A rotary dehumidification rotor comprising a silica gel element containing silica or silica containing iron or aluminum and having a sodium content of 0 to 0.2% by mass as Na 2 O.
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