JP2010162477A - Adsorbent for lower aldehydes and method of manufacturing the same - Google Patents
Adsorbent for lower aldehydes and method of manufacturing the same Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001299 aldehydes Chemical class 0.000 title abstract description 40
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- 239000004202 carbamide Substances 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 92
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 6
- 239000000243 solution Substances 0.000 abstract description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 74
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 46
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
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- 238000000034 method Methods 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
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- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
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- 235000011007 phosphoric acid Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 235000019645 odor Nutrition 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
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- 235000002906 tartaric acid Nutrition 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- -1 platinum group compound Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 241000694440 Colpidium aqueous Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、ホルムアルデヒド、アセトアルデヒドなどの低級アルデヒド類に対し優れた吸着性能を有し、使用期間中担持薬品臭のしない吸着剤に関する。 The present invention relates to an adsorbent that has excellent adsorption performance for lower aldehydes such as formaldehyde and acetaldehyde and does not cause a chemical odor during use.
ホルムアルデヒド、アセトアルデヒドなどのＣ１〜Ｃ４の脂肪族低級アルデヒド類は、いずれも特異な刺激臭を発する有害なガスである。ホルムアルデヒドは、空気中の許容濃度が０．３ｐｐｍと低く、かつ、発ガン性を有すると言われている。また、アセトアルデヒドをはじめとするこれら低級アルデヒド類は我が国では特定悪臭物質に指定され、いずれも嗅覚閾値が非常に低く悪臭公害を引き起こす物質である。
ホルムアルデヒドの発生源としては、ホルムアルデヒドの製造工場および尿素、メラミン、フェノールなどを原料とした樹脂の製造工場のほか、これらの樹脂の加工工場、さらにこれらの樹脂を使用した建材、家具など製造工場などが挙げられる。また、消毒剤としてのホルムアルデヒドや石油類の不完全燃焼排ガス、たばこの副流煙にも含まれている。最近では、室内においても新建材や家具などから発生するホルムアルデヒドが問題になっている。
アセトアルデヒドの発生源としては、アセトアルデヒドおよびその誘導体の製造工場のほか、下水汚泥の加熱処理時にも発生し、またたばこの主流煙中にも含まれている。
C 1 -C 4 aliphatic lower aldehydes such as formaldehyde and acetaldehyde are all harmful gases that emit unique irritating odors. Formaldehyde is said to have an allowable concentration in air as low as 0.3 ppm and has carcinogenic properties. In addition, these lower aldehydes including acetaldehyde are designated as specific malodorous substances in Japan, and all of them are substances that have a very low olfactory threshold and cause odor pollution.
Formaldehyde generation sources include formaldehyde manufacturing plants, resin manufacturing plants made from urea, melamine, phenol, etc., processing plants for these resins, and manufacturing plants for building materials and furniture using these resins. Is mentioned. It is also contained in formaldehyde as a disinfectant, incomplete combustion exhaust gas of petroleum, and sidestream smoke of tobacco. Recently, formaldehyde generated from new building materials and furniture has become a problem even indoors.
As a source of acetaldehyde, it is generated at the time of heat treatment of sewage sludge in addition to the manufacturing plant of acetaldehyde and its derivatives, and is also contained in the mainstream smoke of cigarettes.
近年、これら低級アルデヒド類に対して、作業環境の改善および生活環境の向上などの観点から、有害物質や臭気などが問題視され、この観点から気体、特に空気中の低級アルデヒド類を効率よく除去する吸着剤の開発が強く要望されている。
従来から低級アルデヒド類の吸着剤としては、活性炭、活性アルミナ、シリカゲルなどが挙げられ、なかでも活性炭が広く使用されてきたが、これらの吸着剤自体は、その特性上、ホルムアルデヒド、アセトアルデヒドなどの低級アルデヒド類に対する吸着容量が小さく、寿命が短いという欠点がある。
この改善策として、前記の吸着剤に低級アルデヒド類と反応する化合物、たとえば、脂肪族アミン類、芳香族アミン類などの有機化合物を担持させたものや、触媒として白金族化合物を前記の吸着剤に担持させたものなどが提案されている。
In recent years, harmful substances and odors have been seen as problems with these lower aldehydes from the viewpoint of improving the working environment and living environment. From this viewpoint, gas, especially lower aldehydes in the air are efficiently removed. There is a strong demand for the development of adsorbents.
Conventionally, as adsorbents for lower aldehydes, activated carbon, activated alumina, silica gel and the like have been used, and among them, activated carbon has been widely used. However, these adsorbents themselves have lower properties such as formaldehyde and acetaldehyde. There are drawbacks in that the adsorption capacity for aldehydes is small and the lifetime is short.
As an improvement measure, a compound that reacts with the lower aldehydes on the adsorbent, for example, an organic compound such as an aliphatic amine or an aromatic amine, or a platinum group compound as a catalyst is used as the adsorbent. The one supported on the substrate has been proposed.
しかしながら、有機化合物を担持させた吸着剤は、担持有機化合物の経時安定性、それら自体の有害性、臭気などに問題がある。たとえば、アニリン（沸点１８５℃）を常温付近で単に添着させたもの（特許文献１）は、アニリン自身が発ガン性の疑いがあり、かつ低級アルデヒド類の吸着に対して、経時的に不安定であるなどのために実用化に問題があった。また、活性炭に尿素系化合物の酸含有溶液を含浸、担持させたアルデヒド類吸着剤（特許文献２）やゼオライト、酸性白土、珪藻土、活性炭を尿素、チオ尿素などの水溶液に浸漬、担持させたアルデヒド類吸着剤（特許文献３）などが考案されているが、これらのアルデヒド類吸着剤の製造法は、活性炭などの多孔質担体１ｇ当たり尿素の担持量が１２０ｍｇ以下であり、かつ、多孔質担体１ｇ当たり２０００μＬ以上の尿素水溶液を使用し、多孔質担体に含浸・浸漬する際の温度は常温付近であり、また、少なくとも５０分間以上含浸・浸漬した後、多孔質担体を水溶液から分離し、さらに、１００℃前後で２時間以上乾燥するこれらの工程が必須である。
触媒を担持させたものは、触媒が高価な上、常温では低級アルデヒド類の除去効果が低い。
このように従来の技術は、いずれも低級アルデヒド類の除去に対して満足できるものではなかった。
However, adsorbents carrying organic compounds have problems with the stability of the carried organic compounds over time, their own toxicity, odor, and the like. For example, aniline (boiling point 185 ° C.) simply attached at room temperature (Patent Document 1) is suspected of causing carcinogenicity, and is unstable over time against the adsorption of lower aldehydes. Because of this, there was a problem in practical use. Also, an aldehyde adsorbent (Patent Document 2) impregnated and supported with an acid-containing solution of a urea compound on activated carbon, or an aldehyde immersed in and supported on an aqueous solution of zeolite, acidic clay, diatomaceous earth, activated carbon, or urea. Adsorbents (Patent Document 3) and the like have been devised. The production method of these aldehyde adsorbents is such that the amount of urea supported per 1 g of porous carrier such as activated carbon is 120 mg or less, and the porous carrier A urea aqueous solution of 2000 μL or more per gram is used, and the temperature when impregnating / immersing in the porous carrier is around room temperature, and after impregnating / immersing for at least 50 minutes, the porous carrier is separated from the aqueous solution. These steps of drying at around 100 ° C. for 2 hours or more are essential.
The catalyst-supported catalyst is expensive and has a low effect of removing lower aldehydes at room temperature.
Thus, none of the conventional techniques are satisfactory for the removal of lower aldehydes.
本発明は、熱的に安定で、環境に対して安全であり、かつ、Ｃ１〜Ｃ４の脂肪族低級アルデヒド類を長時間にわたり効率よく吸着除去することができる優れた低級アルデヒド類の吸着剤を提供することを目的としている。 The present invention is excellent in adsorption of lower aldehydes that are thermally stable, safe for the environment, and capable of efficiently adsorbing and removing C 1 -C 4 aliphatic lower aldehydes over a long period of time. The purpose is to provide an agent.
本発明者は、前記の点を鑑み鋭意研究して、多孔質担体１ｇ当たり尿素を１５０〜８００ｍｇおよび不揮発酸を１０〜３００ｍｇ添着した吸着剤が、熱的安定で、環境に対して安全であり、低級アルデヒド類を長期に渡り効率よく吸着除去することを見出した。尿素および不揮発酸を添着する際に、水溶液を４０〜９５℃に加温することで、多孔質担体１ｇ当たり１００〜８００μＬの極少量の水溶液で薬品必要量を完全に溶解できるので、所定量の尿素および不揮発酸を均一に、かつ、簡単に添着することができ、添着後そのままの状態で低級アルデヒド類を非常によく吸着・除去できる。 The present inventor has intensively studied in view of the above points, and the adsorbent impregnated with 150 to 800 mg of urea and 10 to 300 mg of non-volatile acid per 1 g of the porous carrier is thermally stable and safe for the environment. It was found that lower aldehydes can be efficiently adsorbed and removed over a long period of time. When adding urea and non-volatile acid, the required amount of chemical can be completely dissolved in a very small amount of aqueous solution of 100 to 800 μL per 1 g of porous carrier by heating the aqueous solution to 40 to 95 ° C. Urea and non-volatile acids can be uniformly and easily attached, and lower aldehydes can be adsorbed and removed very well as they are after the addition.
本発明で使用される多孔質担体としては、活性炭、活性白土、シリカゲル、活性アルミナ、珪藻土、粘土鉱物などが挙げられ、一般に市販されているものが利用できる。これらの多孔質担体の形状は、破砕状、円柱状、球状、ハニカム状、繊維状などいかなるものでもよい。また、これらの多孔質担体のＢＥＴ比表面積は、５０ｍ２／ｇ以上、好ましくは１００〜２５００ｍ２／ｇのものである。
これらの多孔質担体の中でも疎水性であり、大気中の水分の影響を受けにくい活性炭が特に好ましい。活性炭としては、木炭、コークス、石炭、ヤシ殻、樹脂などを原料として通常の方法により賦活されたものであれば、いかなるものでもよい。
活性炭の表面を予め酸化処理することで低級アルデヒド類の吸着性能が向上する。活性炭の表面を予め酸化する方法としては、たとえば、硝酸、窒素酸化物（ＮＯｘ）、硫酸、硫黄酸化物（ＳＯｘ）、三酸化硫黄、二酸化塩素、過酸化水素、オゾン、酸素含有ガス（たとえば、空気、燃焼排ガスなど）などの酸化剤で、液相あるいは気相で酸化するなどの方法が挙げられる。ＮＯｘやＳＯｘなどの場合は、活性炭にＮＯｘやＳＯｘ含有ガスの吸着、脱着を繰り返すなど方法で活性炭を酸化してもよい。また、酸素含有ガスによる気相酸化などのように活性炭に対する酸化力が弱い場合などでは、ガス中の酸素濃度にもよるが、常温以上の温度、たとえば、２００℃以上、好ましくは２００〜８００℃、さらに好ましくは２５０〜６００℃の温度で行うのが効率的である。
Examples of the porous carrier used in the present invention include activated carbon, activated clay, silica gel, activated alumina, diatomaceous earth, clay mineral, and the like, and commercially available ones can be used. The shape of these porous carriers may be any shape such as a crushed shape, a cylindrical shape, a spherical shape, a honeycomb shape, and a fibrous shape. Further, BET specific surface area of these porous carrier, 50 m 2 / g or more, preferably 100~2500m 2 / g.
Among these porous carriers, activated carbon which is hydrophobic and hardly affected by moisture in the air is particularly preferable. The activated carbon may be any material as long as it is activated by a normal method using charcoal, coke, coal, coconut shell, resin, or the like as a raw material.
The adsorption performance of lower aldehydes is improved by previously oxidizing the surface of the activated carbon. Examples of the method for previously oxidizing the surface of activated carbon include nitric acid, nitrogen oxide (NOx), sulfuric acid, sulfur oxide (SOx), sulfur trioxide, chlorine dioxide, hydrogen peroxide, ozone, oxygen-containing gas (for example, Examples thereof include a method of oxidizing in a liquid phase or a gas phase with an oxidizing agent such as air or combustion exhaust gas. In the case of NOx, SOx, etc., the activated carbon may be oxidized by a method such as repeated adsorption and desorption of NOx and SOx-containing gas on the activated carbon. In addition, when the oxidizing power for activated carbon is weak, such as gas phase oxidation with an oxygen-containing gas, the temperature is higher than room temperature, for example, 200 ° C. or higher, preferably 200 to 800 ° C., depending on the oxygen concentration in the gas. More preferably, it is efficient to carry out at a temperature of 250 to 600 ° C.
このような酸化処理によって活性炭表面に酸素含有基が生成する。本発明での酸化処理において、活性炭に対するこれらの酸化剤使用量は、処理方法や酸化条件（たとえば、処理温度、時間など）などにもよるが、通常、活性炭１ｇ当り酸素原子換算量で１０ｍｇ以上、好ましくは、２０ｍｇ以上、より好ましくは、３０〜２０００ｍｇである。
これらの酸化処理により、活性炭表面に、例えばカルボニル基、カルボキシル基、フェノール性水酸基などの酸素含有基が生成する。この表面酸素含有基は、酸素原子として活性炭全体の１重量％以上、好ましくは、２〜２５重量％以上、さらに好ましくは３〜２０重量％である。
Such an oxidation treatment produces oxygen-containing groups on the activated carbon surface. In the oxidation treatment of the present invention, the amount of these oxidizing agents used for activated carbon depends on the treatment method and oxidation conditions (for example, treatment temperature, time, etc.), but is usually 10 mg or more in terms of oxygen atom per gram of activated carbon. The amount is preferably 20 mg or more, and more preferably 30 to 2000 mg.
By these oxidation treatments, oxygen-containing groups such as a carbonyl group, a carboxyl group, and a phenolic hydroxyl group are generated on the activated carbon surface. This surface oxygen-containing group is 1% by weight or more, preferably 2 to 25% by weight or more, more preferably 3 to 20% by weight of the activated carbon as oxygen atoms.
本発明で使用される不揮発酸は、５０℃、１気圧の下、その蒸気圧が１０ｍｍＨｇ以下のものをいう。たとえば、硫酸、燐酸、ホウ酸などの無機酸、グリコール酸、乳酸、リンゴ酸、酒石酸、クエン酸などの１〜３塩基オキシ酸などが挙げられる。これらの中で１〜３塩基オキシ酸が好ましい。
本発明では、多孔質担体１ｇ当たり尿素を１５０〜８００ｍｇ、好ましくは２００〜５００ｍｇ、および不揮発酸を１０〜３００ｍｇ、好ましくは３０〜２００ｍｇ添着するのが最大の特徴である。このようにすることによって、低級アルデヒド類の吸着性能が飛躍的に向上する。従来技術では、尿素の添着量は多孔質担体１ｇ当たり高々１２０ｍｇである。
また、多孔質担体に尿素および不揮発酸を添着する際にこれらを含む水溶液を４０〜９５℃に加温することも本発明の大きな特徴である。この加温によって多孔質担体１ｇ当たり１００〜８００μＬの極少量の水溶液に薬品必要量を完全に溶解できるので、加温下で多孔質担体に接触させることによって、多量の尿素および不揮発酸を瞬時に多孔質担体に均一に添着できて、かつ、添着後に乾燥しなくてもそのままで低級アルデヒド類を非常によく吸着する吸着剤を得ることができる。
The non-volatile acid used in the present invention is one having a vapor pressure of 10 mmHg or less at 50 ° C. and 1 atm. Examples thereof include inorganic acids such as sulfuric acid, phosphoric acid and boric acid, and 1 to 3 base oxyacids such as glycolic acid, lactic acid, malic acid, tartaric acid and citric acid. Of these, 1-3 base oxyacids are preferred.
The greatest feature of the present invention is that 150 to 800 mg, preferably 200 to 500 mg of urea and 10 to 300 mg, preferably 30 to 200 mg of non-volatile acid are added per 1 g of porous carrier. By doing in this way, the adsorption | suction performance of a lower aldehyde is improved dramatically. In the prior art, the amount of urea added is at most 120 mg per 1 g of porous carrier.
It is also a major feature of the present invention that an aqueous solution containing urea and non-volatile acid is heated to 40 to 95 ° C. when adding urea and non-volatile acid to the porous carrier. This heating can completely dissolve the required amount of chemical in a very small amount of an aqueous solution of 100 to 800 μL per gram of porous carrier, so that a large amount of urea and non-volatile acid can be instantaneously brought into contact with the porous carrier under heating. It is possible to obtain an adsorbent that can be uniformly attached to the porous carrier and adsorbs the lower aldehydes very well as it is without drying after the attachment.
従来技術では、活性炭などの多孔質担体に対して低濃度の尿素水溶液を多量に使用して、多孔質担体をこの水溶液に長時間（たとえば５０分以上）常温付近で浸漬した後、固液分離し、１００℃前後で２時間以上乾燥してはじめてアルデヒドの吸着剤が出来上がるが、アルデヒドの吸着性能は満足できるものではない。 In the prior art, a large amount of low-concentration urea aqueous solution is used for a porous carrier such as activated carbon, and the porous carrier is immersed in this aqueous solution for a long time (for example, 50 minutes or more) at room temperature, followed by solid-liquid separation. However, the aldehyde adsorbent can be obtained only after drying at around 100 ° C. for 2 hours or more, but the aldehyde adsorption performance is not satisfactory.
本発明の低級アルデヒド類吸着剤は、尿素および不揮発酸を含む水溶液を４０〜９５℃に加温して多孔質担体にこれらの薬品を添着することによって容易に得られる。尿素および不揮発酸を含む水溶液の加温は直接的あるいは間接的に通常の方法で行うことができる。尿素および不揮発酸を含む水溶液を４０〜９５℃に加温する時間は、特に限定されない。要は、尿素および不揮発酸を含む水溶液の温度が所定の温度になればよい。尿素および不揮発酸を含む水溶液の加温を９５℃以上にするとこれらの薬品が変質したり、多量の水蒸気が発生したりするので好ましくない。 The lower aldehyde adsorbent of the present invention can be easily obtained by heating an aqueous solution containing urea and non-volatile acid to 40 to 95 ° C. and attaching these chemicals to the porous carrier. Warming of the aqueous solution containing urea and non-volatile acid can be performed directly or indirectly by a usual method. The time for heating the aqueous solution containing urea and non-volatile acid to 40 to 95 ° C. is not particularly limited. In short, it is sufficient that the temperature of the aqueous solution containing urea and the non-volatile acid becomes a predetermined temperature. If the temperature of the aqueous solution containing urea and non-volatile acid is set to 95 ° C. or higher, these chemicals are deteriorated and a large amount of water vapor is generated, which is not preferable.
本発明における除去対象の低級アルデヒド類は、炭素数が６以下で沸点が１００℃以下のアルデヒド、例えばホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、アクロレイン、３−メチル−ブチルアルデヒドを指すが、代表的なものはホルムアルデヒドとアセトアルデヒドである。
本発明においては、上記のようにして得られたアルデヒド類吸着剤を空間内、装置内などに存在させて、アルデヒド類を効率よく除去する方法なども含まれる。アルデヒド類吸着剤を空間内に存在させる場合には、たとえば、アルデヒド類吸着剤をシート状などにしたり、建材に含ませたり、通常よく行われる方法などが挙げられる。また、装置内などに存在させる場合は、塔、容器などに充填したりして、これらにアルデヒド類を含むガスを通気する方法などが考えられる。
The lower aldehydes to be removed in the present invention refer to aldehydes having 6 or less carbon atoms and a boiling point of 100 ° C. or less, such as formaldehyde, acetaldehyde, propionaldehyde, acrolein, and 3-methyl-butyraldehyde. Formaldehyde and acetaldehyde.
The present invention also includes a method for efficiently removing aldehydes by allowing the aldehyde adsorbent obtained as described above to exist in a space or in an apparatus. In the case where the aldehyde adsorbent is present in the space, for example, the aldehyde adsorbent may be formed into a sheet form, included in a building material, or a method that is usually performed. Moreover, when it exists in an apparatus etc., the method etc. which fill a tower, a container, etc., and ventilate the gas containing aldehydes to these are considered.
本発明のアルデヒド吸着剤は、それを使用する常温付近では、無臭でかつ化学的に安定な薬品である、尿素および不揮発酸を多孔質担体に添着するので、添着薬品の臭気や蒸気が漏れ出すようなことは全くなく、しかもアルデヒド類の吸着除去性能は、従来の低級アルデヒド吸着剤に比べて非常に優れており、かつ、安全で、熱劣化や経時劣化も非常に少なく良好である。 The aldehyde adsorbent of the present invention attaches urea and non-volatile acid, which are odorless and chemically stable chemicals, to the porous carrier in the vicinity of the room temperature where the aldehyde adsorbent is used. In addition, the adsorption and removal performance of aldehydes is very superior to that of conventional lower aldehyde adsorbents, and is safe and has very little thermal deterioration and deterioration over time.
以下に実施例及び比較例をあげて、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
８〜３２メッシュの瀝青炭系活性炭Ａ（ＢＥＴ比表面積１１５０ｍ２／ｇ）に対して下記のような処理を施して尿素および不揮発酸を均一に添着した試料を作成した。
試料Ｎｏ．１：尿素１２０ｍｇを燐酸で調整したｐＨ１．５の水溶液５０００μＬ（温度２５℃）に完全に溶解した後、活性炭Ａの１ｇを１時間浸漬した。ろ過した活性炭を１００℃で２時間乾燥した。
試料Ｎｏ．２：水４００μＬに尿素１５０ｍｇおよびクエン酸９０ｍｇを入れ、８０℃に加温してこれらを完全に溶解した。この溶液を活性炭Ａの１ｇに均一に添着し、大気中で１２時間放置した。
試料Ｎｏ．３：尿素３００ｍｇおよびクエン酸９０ｍｇを使用し、水溶液の温度を６０℃にした以外は試料Ｎｏ．２の調製法に準じた。
試料Ｎｏ．４：尿素５００ｍｇおよび酒石酸９０ｍｇを使用し、水溶液の温度を６０℃にした以外は試料Ｎｏ．２の調製法に準じた。
試料Ｎｏ．５：尿素３００ｍｇおよび燐酸５０ｍｇ（９０％正燐酸３０μＬ）を使用し、水溶液の温度を４５℃にした以外は試料Ｎｏ．２の調製法に準じた。
試料Ｎｏ．６：尿素３００ｍｇおよび硫酸１０ｍｇ（９８％濃硫酸５．６μＬ）を使用し、水溶液の温度を４０℃にした以外は試料Ｎｏ．２の調製法に準じた。
試料Ｎｏ．７：尿素３００ｍｇおよびリンゴ酸３００ｍｇを使用し、水溶液の温度を９５℃にした以外は試料Ｎｏ．２の調製法に準じた。
これらの各試料２００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を５５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた値を表１に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
An 8-32 mesh bituminous coal-based activated carbon A (BET specific surface area 1150 m 2 / g) was subjected to the following treatment to prepare a sample in which urea and non-volatile acids were uniformly attached.
Sample No. 1: After 120 mg of urea was completely dissolved in 5000 μL of an aqueous solution of pH 1.5 adjusted with phosphoric acid (temperature 25 ° C.), 1 g of activated carbon A was immersed for 1 hour. The filtered activated carbon was dried at 100 ° C. for 2 hours.
Sample No. 2: 150 mg of urea and 90 mg of citric acid were placed in 400 μL of water and heated to 80 ° C. to completely dissolve them. This solution was uniformly applied to 1 g of activated carbon A and left in the atmosphere for 12 hours.
Sample No. 3: Sample No. 3 was used except that 300 mg of urea and 90 mg of citric acid were used, and the temperature of the aqueous solution was 60 ° C. According to the preparation method of 2.
Sample No. 4: Sample No. 5 was used except that 500 mg of urea and 90 mg of tartaric acid were used and the temperature of the aqueous solution was changed to 60 ° C. According to the preparation method of 2.
Sample No. 5: Sample No. 5 was used except that 300 mg of urea and 50 mg of phosphoric acid (90 μL of normal phosphoric acid 30 μL) were used, and the temperature of the aqueous solution was 45 ° C. According to the preparation method of 2.
Sample No. 6: Sample No. 6 was used except that 300 mg of urea and 10 mg of sulfuric acid (5.6 μL of 98% concentrated sulfuric acid) were used, and the temperature of the aqueous solution was 40 ° C. According to the preparation method of 2.
Sample No. 7: Sample No. 7 was used except that 300 mg of urea and 300 mg of malic acid were used, and the temperature of the aqueous solution was 95 ° C. According to the preparation method of 2.
200 mg of each of these samples was weighed into a 3 L tetrabag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 550 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. The values obtained by the following formula as acetaldehyde removal performance are shown in Table 1.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
実施例１の各試料１００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のホルムアルデヒド水溶液を注入して、各テトラバッグ中のホルムアルデヒド濃度（Ｃ０）を２００ｐｐｍとした。２４時間後の各テトラバッグ中のホルムアルデヒド濃度（Ｃ）を測定した。ホルムアルデヒド除去性能として次式で求めた値を表２に示した。
ホルムアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
100 mg of each sample of Example 1 was weighed into a 3 L tetra bag and filled with air. A predetermined amount of an aqueous formaldehyde solution was injected into each tetrabag to adjust the formaldehyde concentration (C 0 ) in each tetrabag to 200 ppm. The formaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 2 shows the value obtained by the following formula as the formaldehyde removal performance.
Formaldehyde removal performance = (1-C / C 0 ) × 100 (%)
市販の活性白土（和光純薬）に水を加えてよく練合し、１ｍｍφの円柱状に成型し、これを１００℃で乾燥し、さらに空気中にて４５０℃で１時間焼成した。このようにして得られた活性白土焼成ペッレトＢ（ＢＥＴ比表面積４５０ｍ２／ｇ）に対して下記のような処理を施して尿素および不揮発酸を均一に添着した試料を作成した。
試料Ｎｏ．８：尿素１２０ｍｇを燐酸で調整したｐＨ１．５の水溶液５０００μＬ（温度２５℃）に完全に溶解した後、活性白土焼成ペッレトＢの１ｇを１時間浸漬した。ろ過した活性白土焼成ペッレトを１００℃で２時間乾燥した。
試料Ｎｏ．９：水４００μＬに尿素１５０ｍｇおよび燐酸５０ｍｇ（９０％正燐酸３０μＬ）を入れ、８０℃に加温してこれらを完全に溶解し、活性白土焼成ペッレトＢの１ｇに均一に添着し、大気中で１２時間放置した。
試料Ｎｏ．１０：尿素３００ｍｇおよびクエン酸８０ｍｇを使用した以外は試料Ｎｏ．９の調製法に準じた。
これらの各試料４００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を５５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた値を表３に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
Water was added to a commercially available activated clay (Wako Pure Chemicals), kneaded well, formed into a 1 mmφ cylindrical shape, dried at 100 ° C., and further fired at 450 ° C. for 1 hour in air. The activated clay baked pellets B (BET specific surface area 450 m 2 / g) thus obtained were subjected to the following treatment to prepare a sample in which urea and non-volatile acids were uniformly attached.
Sample No. 8: After completely dissolving 120 mg of urea in 5000 μL of an aqueous solution of pH 1.5 adjusted with phosphoric acid (temperature 25 ° C.), 1 g of activated clay calcined pellet B was immersed for 1 hour. The filtered activated clay calcined pellets were dried at 100 ° C. for 2 hours.
Sample No. 9: Put urea 150 mg and phosphoric acid 50 mg (90% orthophosphoric acid 30 μL) in 400 μL of water, heat to 80 ° C. to completely dissolve them, and evenly adhere to 1 g of activated clay baked pellets B in the atmosphere. Left for 12 hours.
Sample No. 10: Sample No. except that 300 mg of urea and 80 mg of citric acid were used. The preparation method of 9 was followed.
400 mg of each of these samples was weighed into a 3 L tetrabag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 550 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 3 shows values obtained by the following formula as acetaldehyde removal performance.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
８〜３２メッシュのヤシ殻系活性炭Ｃ（ＢＥＴ比表面積１２００ｍ２／ｇ）の各３０ｇを５５ｍｍφの石英ガラス管に充填して、それぞれ２５０、４００、５００、および６００℃の各温度でＯ２−１０.０ｖｏｌ％含有のＮ２ガスを線流速５ｃｍ／秒で２０分間流通した後、Ｎ２ガス中で常温まで冷却して、活性炭Ｄ、Ｅ、ＦおよびＧを得た。
酸化処理をした活性炭Ｄ、Ｅ、ＦおよびＧについて、次の方法で測定した表面酸化物又は酸素含有基の酸素量は、それぞれ５．５重量％、８．９重量％、１２．３重量％および１６．１重量％であった。なお、酸化処理をしない活性炭Ｃの酸素量は０．７重量％であった。
「活性炭の表面酸化物の測定法」
直径２０ｍｍ×長さ１０００ｍｍの石英カラムに試料活性炭３ｇを入れ、試料の前後は十分に乾燥させた石英ガラスウールに固定し、電気環状炉にセットした。また石英カラムにはゴム栓で前後に蓋をして窒素を導入するための孔と排出するための孔を空ける。１００ｍＬ／分の流速で窒素を石英カラムに流しながら、１００℃まで加熱昇温し、次いで、出口ガスをテトラバックに接続し、４００℃／時間の昇温速度で９００℃まで加熱昇温した。９００℃になってから、さらに３０分間９００℃で保持した後、テトラバックを外し、捕集したガス量を測定するとともに、捕集されたガスにおけるＣＯとＣＯ2の総濃度を、メタンコンバータ付きのＦＩＤ検出器付ガスクロマトグラフィーで測定し、表面酸素の含量を算出した。
これらの各活性炭１ｇに対して水４００μＬに尿素３００ｍｇおよびクエン酸８０ｍｇを溶解した８０℃の水溶液を用いて均一に添着し、大気中で１２時間放置した。
このようにして得られたこれらの吸着剤各１００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を５５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた結果を表４に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
Each 30 g of 8-32 mesh coconut shell activated carbon C (BET specific surface area 1200 m 2 / g) was filled into a 55 mmφ quartz glass tube, and O 2 − at each temperature of 250, 400, 500, and 600 ° C. After flowing 10.0 vol% of N 2 gas at a linear flow rate of 5 cm / sec for 20 minutes, it was cooled to room temperature in N 2 gas to obtain activated carbon D, E, F, and G.
For the activated carbons D, E, F and G subjected to oxidation treatment, the amounts of oxygen in the surface oxides or oxygen-containing groups measured by the following methods were 5.5% by weight, 8.9% by weight and 12.3% by weight, respectively. And 16.1% by weight. The oxygen content of the activated carbon C that was not oxidized was 0.7% by weight.
"Measurement method of surface oxide of activated carbon"
3 g of sample activated carbon was placed in a quartz column having a diameter of 20 mm and a length of 1000 mm, and the sample was fixed on quartz glass wool that had been sufficiently dried before and after the sample and set in an electric annular furnace. In addition, the quartz column has a hole for introducing nitrogen and a hole for discharging nitrogen by capping the front and back with rubber stoppers. While flowing nitrogen through the quartz column at a flow rate of 100 mL / min, the temperature was raised to 100 ° C., and then the outlet gas was connected to a tetra-buck and heated to 900 ° C. at a rate of 400 ° C./hour. After reaching 900 ° C., hold at 900 ° C. for another 30 minutes, then remove the tetraback, measure the amount of gas collected, and add the total concentration of CO and CO 2 in the collected gas with a methane converter. The surface oxygen content was calculated by gas chromatography with FID detector.
1 g of each activated carbon was uniformly added using an aqueous solution at 80 ° C. in which 300 mg of urea and 80 mg of citric acid were dissolved in 400 μL of water, and left in the atmosphere for 12 hours.
100 mg of each of these adsorbents thus obtained was weighed into a 3 L tetrabag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 550 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 4 shows the results obtained by the following formula as the acetaldehyde removal performance.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
５００ｍＬのビーカーに５重量％の過酸化水素水１００ｍＬを入れ、８０℃の水浴中で８０℃に加熱した。この過酸化水素水に実施例１の瀝青炭系活性炭Ａの１０ｇを入れて攪拌しながら３０分間酸化した。酸化後の活性炭をろ過して１００℃で乾燥した。酸化処理をした活性炭Ｈの表面酸素量は、８．５重量％であった。なお、未酸化の活性炭Ａのそれは、０．９重量％である。
活性炭ＡおよびＨの１ｇに対して水４００μＬに尿素３００ｍｇおよび酒石酸１００ｍｇを溶解した８０℃の水溶液を用いて均一に添着し、大気中で１２時間放置した。
このようにして得られたこれらの吸着剤各１００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を５５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた結果を表５に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
A 500 mL beaker was charged with 100 mL of 5 wt% hydrogen peroxide and heated to 80 ° C in an 80 ° C water bath. In this hydrogen peroxide solution, 10 g of the bituminous coal-based activated carbon A of Example 1 was added and oxidized for 30 minutes while stirring. The oxidized activated carbon was filtered and dried at 100 ° C. The surface oxygen amount of the activated carbon H subjected to the oxidation treatment was 8.5% by weight. The unoxidized activated carbon A is 0.9% by weight.
An aqueous solution at 80 ° C. in which 300 mg of urea and 100 mg of tartaric acid were dissolved in 400 μL of water per 1 g of activated carbon A and H was uniformly added, and left in the atmosphere for 12 hours.
100 mg of each of these adsorbents thus obtained was weighed into a 3 L tetrabag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 550 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 5 shows the results obtained by the following formula as acetaldehyde removal performance.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
内径９４ｍｍφのアクリル製カラムに実施例４のヤシ殻系活性炭Ｃ１００ｍＬをステンレス金網容器に入れて、活性炭充填層を形成した。この活性炭層にオゾン約１８０ｐｐｍ含有の空気を流量５Ｌ／分で２日間流通し、気相でのオゾン酸化処理活性炭Ｉを得た。この活性炭の表面酸素量は８．０重量％であった。
活性炭ＣおよびＩについて実施例５と同様な方法で、それぞれ活性炭ＣおよびＩの１ｇに対して水４００μＬに尿素３００ｍｇおよび乳酸５０ｍｇを溶解した８０℃の水溶液を用いて均一に添着し、大気中で１２時間放置した。
このようにして得られたこれらの吸着剤各１００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を５５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた結果を表６に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
100 mL of coconut shell activated carbon C of Example 4 was placed in a stainless steel wire mesh container in an acrylic column having an inner diameter of 94 mmφ to form an activated carbon packed layer. Air containing about 180 ppm of ozone was passed through the activated carbon layer at a flow rate of 5 L / min for 2 days to obtain ozone-oxidized activated carbon I in the gas phase. The surface oxygen content of this activated carbon was 8.0% by weight.
Activated carbons C and I were uniformly added using an aqueous solution at 80 ° C. in which 300 mg of urea and 50 mg of lactic acid were dissolved in 400 μL of water for 1 g of activated carbons C and I, respectively, in the same manner as in Example 5. Left for 12 hours.
100 mg of each of these adsorbents thus obtained was weighed into a 3 L tetrabag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 550 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 6 shows the results obtained by the following formula as the acetaldehyde removal performance.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
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| WO2020162091A1 (en) * | 2019-02-06 | 2020-08-13 | 孝章 下原 | Formaldehyde scavenger |
| US11298681B2 (en) | 2018-03-01 | 2022-04-12 | 3M Innovative Properties Company | Urea-impregnated zeolite sorbents and method for making the same |
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| CN102101040A (en) * | 2011-01-28 | 2011-06-22 | 河北亚太环境科技发展股份有限公司 | Polyfunctional formaldehyde adsorption material |
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