JP2007021412A - Adsorbing and removing agent for organic compound - Google Patents
Adsorbing and removing agent for organic compound Download PDFInfo
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- JP2007021412A JP2007021412A JP2005208905A JP2005208905A JP2007021412A JP 2007021412 A JP2007021412 A JP 2007021412A JP 2005208905 A JP2005208905 A JP 2005208905A JP 2005208905 A JP2005208905 A JP 2005208905A JP 2007021412 A JP2007021412 A JP 2007021412A
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- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 49
- 229940100890 silver compound Drugs 0.000 claims abstract description 44
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 44
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 150000001299 aldehydes Chemical class 0.000 claims abstract 2
- 238000001179 sorption measurement Methods 0.000 claims description 34
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 31
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 24
- 229910001923 silver oxide Inorganic materials 0.000 claims description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 239000007789 gas Substances 0.000 abstract description 16
- 150000004653 carbonic acids Chemical class 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 63
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 63
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 14
- 238000005342 ion exchange Methods 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 14
- 235000013980 iron oxide Nutrition 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910001961 silver nitrate Inorganic materials 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920002620 polyvinyl fluoride Polymers 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 229910006540 α-FeOOH Inorganic materials 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- OVMJVEMNBCGDGM-UHFFFAOYSA-N iron silver Chemical compound [Fe].[Ag] OVMJVEMNBCGDGM-UHFFFAOYSA-N 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical group O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- -1 α-FeOOH Chemical compound 0.000 description 1
- 229910003153 β-FeOOH Inorganic materials 0.000 description 1
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 1
Abstract
Description
本発明は、アルデヒド類、カルボン酸類、アミン類の吸着性能に優れた有機化合物吸着除去剤に関し、更に詳しくは、常温で長期にわたって吸着性能を維持できる有機化合物吸着除去剤に関する。 The present invention relates to an organic compound adsorption / removal agent having excellent adsorption performance for aldehydes, carboxylic acids, and amines, and more particularly to an organic compound adsorption / removal agent capable of maintaining adsorption performance for a long period at room temperature.
従来より、建物の室内や自動車の車内等におけるタバコ臭の除去を主目的として、空気清浄機や脱臭剤が広く用いられている。これらは、タバコ臭の主成分であるアセトアルデヒド、あるいは、シックハウスの原因物質であるホルムアルデヒド等の吸着除去等を目的とするものであり、多くの吸着剤の検討がなされている。その中でも、活性炭は各種有機物質を吸着する材料として古くから知られているが、低分子で高極性の有機物（例えば、アセトアルデヒド、ホルムアルデヒド等）は十分吸着することができず、上述の用途に用いる場合は、活性炭にアミン類やアスコルビン酸等を担持させて吸着能を高めたものが用いられている。 Conventionally, air purifiers and deodorizing agents have been widely used mainly for the purpose of removing tobacco odors in the interior of buildings or in automobiles. These are intended to adsorb and remove acetaldehyde, which is the main component of tobacco odor, or formaldehyde, which is a causative substance of sick house, and many adsorbents have been studied. Among them, activated carbon has long been known as a material that adsorbs various organic substances, but low molecular and high polarity organic substances (for example, acetaldehyde, formaldehyde, etc.) cannot be adsorbed sufficiently, and are used for the above-mentioned applications. In this case, activated carbon is used in which amines, ascorbic acid or the like is supported on activated carbon to enhance the adsorption ability.
このように、アミン類を担持させたものとしては、例えば、アニリンを用いたものや（例えば特許文献１参照）、エタノール系アミン等を用いたものが開示されている（例えば特許文献２参照）。
しかしながら、アミン類を担持させる技術は、担持アミン類の状態は不安定であることから、熱的および経時的な化学変化による失活が起こりやすく、長期にわたって満足すべき除去性能を発現することが困難であるという問題がある。また、アスコルビン酸においても、吸湿すると空気中で容易に酸化分解され、失活してしまい性能劣化が起こるという問題がある。 However, the technology for supporting amines is unstable in the state of the supported amines, and thus is easily deactivated due to thermal and chemical changes over time, and can exhibit satisfactory removal performance over a long period of time. There is a problem that it is difficult. In addition, ascorbic acid also has a problem that when it absorbs moisture, it is easily oxidized and decomposed in the air and deactivated, resulting in performance deterioration.
一方、アルデヒド類ガスを除去する方法として、酸化鉄等の金属酸化物を用いる方法が近年注目を集めている。前記金属酸化物として、例えば、酸化鉄、銀を担持したアルミナがある（例えば非特許文献１参照）。 On the other hand, as a method for removing aldehyde gases, a method using a metal oxide such as iron oxide has recently attracted attention. Examples of the metal oxide include alumina supporting iron oxide and silver (see Non-Patent Document 1, for example).
しかしながら、かかる酸化鉄、もしくは 銀担持アルミナは、十分な除去活性を得るためには、高温条件が必要であり、一般生活における温湿度領域では、除去活性が低く、十分な除去性能が得られないという問題がある。
また、銀酸化物粒子とマンガン酸化物粒子からなるマンガン酸化物含有物、および、酸化鉄によるホルムアルデヒドの分解除去が開示されている（例えば特許文献３参照）。しかしながら、かかるマンガン酸化物含有物は、ＰＲＴＲ第一種指定化学物質であるマンガン酸化物が含有されており、環境汚染の懸念があるという問題がある。また、開示されている酸化鉄（Ｆｅ２Ｏ３）のみでは、一般生活における温湿度領域では活性が低く、十分な除去性能を得られないという問題がある。
また、吸着性多孔質担体に銀及び／又は銀化合物を担持して成ることを特徴とする悪臭物質除去用触媒が開示されている（例えば特許文献４参照）。しかしながら、かかる悪臭物質除去用触媒における、銀及び／又は銀化合物の担持体としては、ゼオライト、アルミナ等の吸着性多孔質体であり、担持体としての鉄酸化物に関する言及は一切なされておらず、また、担持体がゼオライト、アルミナでは一般生活における温湿度領域における活性が低く、十分な除去性能を得られないという問題がある。
上述のとおり、一般生活における温湿度領域で、長期にわたってアルデヒド類、カルボン酸類、アミン類から選ばれる少なくとも一種以上のガス状有機化合物を含むガスを除去する有機化合物吸着除去剤において、環境汚染への影響が低く、かつ、その除去性能を維持できる有機化合物吸着除去剤は見当たらないのが現状である。ここで言う、一般生活における温湿度領域とは、温度範囲でおおよそ−３０〜５０℃、湿度範囲でおおよそ２０〜９５ＲＨ％のことである。 As described above, an organic compound adsorption / removal agent that removes a gas containing at least one gaseous organic compound selected from aldehydes, carboxylic acids, and amines over a long period of time in a temperature and humidity range in general life. At present, there is no organic compound adsorption / removal agent that has a low influence and can maintain its removal performance. The temperature / humidity region in general life referred to here is approximately −30 to 50 ° C. in the temperature range and approximately 20 to 95 RH% in the humidity range.
本発明は上記従来技術の課題を背景になされたものであり、アルデヒド類、カルボン酸類、アミン類から選ばれる少なくとも一種以上のガス状有機化合物を含むガスの、一般生活における温湿度領域で長期にわたって満足すべき除去性能を発現することができ、かつ、環境汚染への影響が低い有機化合物吸着除去剤を提供することを目的とする。 The present invention has been made against the background of the problems of the prior art described above, and is a gas containing at least one gaseous organic compound selected from aldehydes, carboxylic acids, and amines over a long period of time in a temperature and humidity range in general life. An object of the present invention is to provide an organic compound adsorption / removal agent that can exhibit satisfactory removal performance and has a low influence on environmental pollution.
本発明者らは上記課題を解決するため、鋭意研究した結果、遂に本発明を完成するに到った。すなわち本発明は、（１）アルデヒド類、カルボン酸類、アミン類から選ばれる少なくとも一種以上のガス状有機化合物を含むガスを除去する有機化合物吸着除去剤において、前記有機化合物吸着除去剤が少なくとも銀化合物を担持した鉄化合物粒子を含有し、前記銀化合物の担持量が銀化合物と鉄化合物粒子の合計量に対して０．１〜５０重量％であり、（２）前記鉄化合物粒子がＢＥＴ比表面積５０ｍ2／ｇ以上の鉄酸化物であることを特徴とする（１）に記載の有機化合物吸着除去剤であり、（３）前記銀化合物粒子が銀酸化物であることを特徴とする（１）（２）のいずれかに記載の有機化合物吸着除去剤である。 As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention provides (1) an organic compound adsorption / removal agent that removes a gas containing at least one gaseous organic compound selected from aldehydes, carboxylic acids, and amines, wherein the organic compound adsorption / removal agent is at least a silver compound The amount of the silver compound supported is 0.1 to 50% by weight based on the total amount of the silver compound and the iron compound particles, and (2) the iron compound particles have a BET specific surface area. The organic compound adsorption / removal agent according to (1), which is an iron oxide of 50 m 2 / g or more, and (3) the silver compound particles are silver oxide (1) ) The organic compound adsorption remover according to any one of (2).
本発明によるアルデヒド類、カルボン酸類、アミン類から選ばれる少なくとも一種以上のガス状有機化合物を含むガスを除去する有機化合物吸着除去剤は、少なくとも銀化合物を担持した鉄化合物粒子を含有し、前記銀化合物の担持量が銀化合物と鉄化合物粒子の合計量に対して０．１〜５０重量％であるため、一般生活における温湿度領域での高い除去性能、かつ、長期にわたって満足すべき除去性能を発現することが可能であり、また、環境汚染への影響が少ないという利点を有する。 An organic compound adsorption removing agent for removing a gas containing at least one gaseous organic compound selected from aldehydes, carboxylic acids, and amines according to the present invention contains at least iron compound particles carrying a silver compound, and the silver Since the compound loading is 0.1 to 50% by weight based on the total amount of silver compound and iron compound particles, high removal performance in the temperature and humidity range in general life and satisfactory removal performance over a long period of time It has the advantage that it can be expressed and has little impact on environmental pollution.
以下、本発明を詳細に説明する。本発明は、アルデヒド類、カルボン酸類、アミン類から選ばれる少なくとも一種以上のガス状有機化合物を含むガスを除去する有機化合物吸着除去剤において、前記有機化合物吸着除去剤が少なくとも銀化合物を担持した鉄化合物粒子を含有することが好ましい。銀化合物を担持していない鉄化合物粒子では一般生活における温湿度領域において十分な除去性能は実現できない。しかしながら、鉄化合物粒子に銀化合物を担持させると、その相乗効果により非常に高い除去性能を実現することができることを本発明者は見出した。相乗効果のメカニズムは明確ではないが、次の（１）〜（４）のように推測される。つまり、最初に、（１）ガス状有機化合物が鉄化合物粒子上に捕捉される、さらに、（２）鉄化合物粒子上に捕捉されたガス状有機化合物が鉄の電子授受作用により活性化され分解されやすい状態になる、最後に、（３）そのごく近傍に位置する銀化合物により、鉄化合物粒子上で活性化されたガス状有機化合物が分解される、その際、（４）銀化合物においても、担持体である鉄化合物粒子からの電子授受作用を受け、その分解力が向上していると考えられる。 Hereinafter, the present invention will be described in detail. The present invention relates to an organic compound adsorption / removal agent for removing a gas containing at least one gaseous organic compound selected from aldehydes, carboxylic acids, and amines, wherein the organic compound adsorption / removal agent is an iron carrying at least a silver compound. It is preferable to contain compound particles. With iron compound particles that do not carry a silver compound, sufficient removal performance cannot be realized in the temperature and humidity range in general life. However, the present inventor has found that when a silver compound is supported on iron compound particles, very high removal performance can be realized due to its synergistic effect. The mechanism of the synergistic effect is not clear, but is presumed as the following (1) to (4). That is, first, (1) the gaseous organic compound is trapped on the iron compound particles, and (2) the gaseous organic compound captured on the iron compound particles is activated and decomposed by the electron transfer function of iron. Finally, (3) the gaseous organic compound activated on the iron compound particles is decomposed by the silver compound located in the immediate vicinity thereof. At that time, (4) also in the silver compound It is considered that the decomposing power is improved by receiving and receiving an electron from the iron compound particles as the support.
銀化合物の担持量については、銀化合物と鉄化合物粒子の合計量に対して０．１〜５０重量％であることが好ましい。より好ましくは、０．１〜３０重量％である。銀化合物の担持量が５０重量％より大きいと、鉄化合物粒子が銀化合物により被覆され、前記相乗効果のメカニズムおける（１）、および、（２）が阻害されてしまい、相乗効果が小さくなり、その結果、十分な除去性能が実現できなくなる。一方で、銀化合物の担持量が０．１重量％より小さいと、銀化合物が少な過ぎるため、前記相乗効果のメカニズムにおける（３）の影響が小さくなり、結果として、十分な除去性能が実現できなくなる。 The supported amount of the silver compound is preferably 0.1 to 50% by weight with respect to the total amount of the silver compound and the iron compound particles. More preferably, it is 0.1 to 30% by weight. When the loading amount of the silver compound is larger than 50% by weight, the iron compound particles are coated with the silver compound and (1) and (2) in the mechanism of the synergistic effect are hindered, and the synergistic effect is reduced. As a result, sufficient removal performance cannot be realized. On the other hand, if the supported amount of the silver compound is less than 0.1% by weight, the amount of the silver compound is too small, and the influence of (3) in the mechanism of the synergistic effect is reduced, and as a result, sufficient removal performance can be realized. Disappear.
本発明における鉄化合物粒子は鉄酸化物であることが好ましい。鉄酸化物であれば、低温での高い除去性能を実現することができることを本発明者は見出したからである。鉄酸化物の種類については、特に定めないが、ＦｅＯ、Ｆｅ3Ｏ4、Ｆｅ2Ｏ3等の酸化鉄、α−ＦｅＯＯＨ、β−ＦｅＯＯＨ、γ−ＦｅＯＯＨ等のオキシ水酸化鉄、Ｆｅ（ＯＨ）3等の水酸化鉄、Ｋ2ＦｅＯ4等の鉄酸塩化合物等、もしくは、それらの複合体、および、異種金属と鉄との複合酸化物等が挙げられる。 The iron compound particles in the present invention are preferably iron oxides. This is because the present inventor has found that high removal performance at low temperatures can be realized with iron oxide. The type of the iron oxide is not particularly defined, but iron oxide such as FeO, Fe 3 O 4 and Fe 2 O 3 , iron oxyhydroxide such as α-FeOOH, β-FeOOH and γ-FeOOH, Fe (OH ) iron hydroxide 3 such as K 2 FeO ferrate compounds such 4 or the like, or complexes thereof, and composite oxides of different metals and iron, and the like.
前記鉄化合物粒子のＢＥＴ比表面積は、５０ｍ2／ｇ以上であることが好ましい。ＢＥＴ比表面積が５０ｍ2／ｇ以上であれば、低温での高い除去性能を実現することができることを本発明者は見出したからである。より好ましくは１００ｍ2／ｇ以上である。最も好ましくは１５０ｍ2／ｇ以上である。ＢＥＴ比表面積の上限は特に限定するものではないが、１０００ｍ2／ｇ以下であることが好ましい。この範囲を超えると、除去性能はほとんど変化しない一方で、製造が非常に困難になるという不都合が生じるからである。 The iron compound particles preferably have a BET specific surface area of 50 m 2 / g or more. This is because the present inventor has found that if the BET specific surface area is 50 m 2 / g or more, high removal performance at a low temperature can be realized. More preferably, it is 100 m 2 / g or more. Most preferably, it is 150 m 2 / g or more. The upper limit of the BET specific surface area is not particularly limited, but is preferably 1000 m 2 / g or less. If this range is exceeded, the removal performance is hardly changed, but the disadvantage is that manufacturing becomes very difficult.
本発明における鉄化合物粒子の製造方法は特に定めず、一般的な製造方法が適用できるが、好ましくは、二価、もしくは、三価の鉄塩水溶液に酸化剤を添加した後、アルカリ化合物を用いて沈殿物を生成し、これを溶液と分離した後、乾燥させる方法である。高温での焼成処理が必要でないため、比較的簡便に製造できるという利点を有するからである。 The production method of the iron compound particles in the present invention is not particularly defined, and a general production method can be applied. Preferably, an alkaline compound is used after adding an oxidizing agent to a divalent or trivalent iron salt aqueous solution. In this method, a precipitate is formed, separated from the solution, and then dried. This is because a baking process at a high temperature is not necessary, so that it has an advantage that it can be manufactured relatively easily.
本発明における銀化合物は銀酸化物であることが好ましい。銀化合物が金属銀、硫化銀、塩化銀等の酸化物でない場合は、低温での高い除去性能を実現することができないが、銀化合物が銀酸化物であれば、低温での高い除去性能を実現することができることを本発明者は見出したからである。銀酸化物の種類については、特に定めないが、Ａｇ2Ｏ、ＡｇＯ等の酸化物、もしくは、それらの複合体が挙げられる。 The silver compound in the present invention is preferably a silver oxide. If the silver compound is not an oxide such as metallic silver, silver sulfide, or silver chloride, high removal performance at low temperatures cannot be realized. However, if the silver compound is silver oxide, high removal performance at low temperatures is not possible. This is because the present inventors have found that this can be realized. The type of silver oxide is not particularly defined, and examples thereof include oxides such as Ag 2 O and AgO, or composites thereof.
本発明における銀化合物を担持した鉄化合物粒子の製造方法は特に限定されず、一般的な製造方法が適用できる。好ましくは、鉄酸化物粒子を銀塩水溶液中に懸濁させながら、塩基性水溶液を添加して製造する方法である。高温での焼成処理が必要でないため生成した銀酸化物が金属銀に還元され失活することがないうえに、簡便に製造できるという利点を有するからである。また、塩基性水溶液を添加する前に銀塩水溶液中に界面活性剤を添加することが好ましい。界面活性剤を添加すれば、生成する酸化銀の粒径が小さくなり、結果として、均一に、かつ、高分散した状態で酸化銀を鉄酸化物粒子上に担持することができることを本発明者は見出したからである。添加する界面活性剤としては、特に定めないが、シクロデキストリン、ポリビニルアルコール等のヒドロキシル基を多く含有するものが好ましい。ヒドロキシル基の水素原子と銀酸化物の酸素原子との水素結合作用が、銀酸化物同士の凝集を防ぐことを本発明者は見出したからである。 The manufacturing method of the iron compound particle | grains which carry | supported the silver compound in this invention is not specifically limited, A general manufacturing method is applicable. Preferably, it is a method of producing by adding a basic aqueous solution while suspending iron oxide particles in an aqueous silver salt solution. This is because there is an advantage that the produced silver oxide is not reduced to metallic silver and is not deactivated because it is not required to be fired at a high temperature, and it can be easily produced. Moreover, it is preferable to add a surfactant in the aqueous silver salt solution before adding the basic aqueous solution. If the surfactant is added, the particle size of the silver oxide to be produced becomes small, and as a result, the present inventor can support the silver oxide on the iron oxide particles in a uniformly and highly dispersed state. Because I found it. The surfactant to be added is not particularly defined, but those containing a large number of hydroxyl groups such as cyclodextrin and polyvinyl alcohol are preferred. This is because the present inventors have found that the hydrogen bonding action between the hydrogen atom of the hydroxyl group and the oxygen atom of the silver oxide prevents aggregation of the silver oxides.
以下、実施例によって本発明の作用効果をより具体的に示す。下記実施例は本発明方法を限定する性質のものではなく、前・後記の趣旨に沿って設計変更することはいずれも本発明の技術的範囲に含まれるものである。 Hereinafter, the effects of the present invention will be described more specifically by way of examples. The following examples are not intended to limit the method of the present invention, and any design changes in accordance with the gist of the preceding and following descriptions are included in the technical scope of the present invention.
（ＢＥＴ比表面積の測定方法）
有機化合物吸着除去剤を約１００ｍｇ採取し、１２０℃で１２時間真空乾燥の後、秤量した。自動比表面積装置ジェミニ２３７５（マイクロメリティックス社製）を使用し、液体窒素の沸点（−１９５．８℃）における窒素ガスの吸着量を相対圧が０．０２〜０．９５の範囲で徐々に高めながら４０点測定し、上記サンプルの吸着等温線を作製した。相対圧０．０２〜０．１５での結果をＢＥＴプロットし、重量当りのＢＥＴ比表面積［ｍ2／ｇ］を求めた。
(Measurement method of BET specific surface area)
About 100 mg of the organic compound adsorption removing agent was sampled and vacuum-dried at 120 ° C. for 12 hours, and then weighed. Using an automatic specific surface area device Gemini 2375 (manufactured by Micromeritics), the adsorption amount of nitrogen gas at the boiling point of liquid nitrogen (-195.8 ° C.) is gradually increased in a range of relative pressure of 0.02 to 0.95. The sample was measured at 40 points while increasing the temperature to obtain an adsorption isotherm of the sample. The results at a relative pressure of 0.02 to 0.15 were BET-plotted to determine the BET specific surface area [m 2 / g] per weight.
（ホルムアルデヒド除去性能の測定方法）
有機化合物吸着除去剤１００ｍｇを、両側をグラスフィルターで挟んで内径１５ｍｍφのガラスカラムに充填した。これにホルムアルデヒド２ｐｐｍを含む２５℃、５０ＲＨ％の空気を１Ｌ／分で連続的に流通させた。試料の雰囲気温度は２５℃とした。試料の入口・出口側のガスを一定時間毎にサンプリングし、ガスクロマトグラフにてホルムアルデヒド濃度を測定し、その比から除去率を算出した。この除去率が２０％以下になるまで流通、濃度測定を続けた。ホルムアルデヒド供給量（濃度、流量、温度から計算）に対する除去率の曲線を積分することによりホルムアルデヒド吸着量［ｍｇ］を求め、これを試料の重量で割ることにより、吸着容量［ｍｇ／ｇ］を算出した。
(Method for measuring formaldehyde removal performance)
100 mg of organic compound adsorption removing agent was packed in a glass column having an inner diameter of 15 mm with both sides sandwiched by glass filters. To this, air at 25 ° C. and 50 RH% containing 2 ppm of formaldehyde was continuously circulated at 1 L / min. The ambient temperature of the sample was 25 ° C. The gas at the inlet and outlet sides of the sample was sampled at regular intervals, the formaldehyde concentration was measured with a gas chromatograph, and the removal rate was calculated from the ratio. Distribution and concentration measurement were continued until the removal rate was 20% or less. The amount of formaldehyde adsorbed [mg] is obtained by integrating the removal rate curve with the formaldehyde supply amount (calculated from concentration, flow rate, and temperature), and this is divided by the weight of the sample to calculate the adsorption capacity [mg / g]. did.
（酢酸除去性能の測定方法）
５Ｌのテドラーバッグ中に酢酸ガス１００ｐｐｍを含む２５℃、５０ＲＨ％の空気、有機化合物吸着除去剤３０ｍｇを封入した。中に入っている有機化合物吸着除去剤と酢酸を含む空気が十分に接触、反応するように、テドラーバッグを適宜振った。なお、テドラーバッグ周囲の雰囲気温度は２５℃とした。３時間後のテドラーバッグ内の酢酸ガス濃度をＦＩＤ付きガスクロマトグラフにて測定し、反応前後の酢酸の濃度変化から酢酸除去量［ｍｇ］を求め、これを試料の重量で割ることにより、除去容量［ｍｇ／ｇ］を算出した。
(Measurement method of acetic acid removal performance)
In a 5 L Tedlar bag, 25 mg of air containing 100 ppm of acetic acid gas, 50 RH% air, and 30 mg of an organic compound adsorption removing agent were sealed. The Tedlar bag was shaken as appropriate so that the organic compound adsorption / removal agent contained therein and the air containing acetic acid were in sufficient contact and reaction. The ambient temperature around the Tedlar bag was 25 ° C. The acetic acid gas concentration in the Tedlar bag after 3 hours was measured with a gas chromatograph with FID, and the acetic acid removal amount [mg] was determined from the change in acetic acid concentration before and after the reaction. mg / g] was calculated.
（トリメチルアミン除去性能の測定方法）
５Ｌのテドラーバッグ中にトリメチルアミンガス１００ｐｐｍを含む２５℃、５０ＲＨ％の空気、有機化合物吸着除去剤３０ｍｇを封入した。中に入っている有機化合物吸着除去剤とトリメチルアミンを含む空気が十分に接触、反応するように、テドラーバッグを適宜振った。なお、テドラーバッグ周囲の雰囲気温度は２５℃とした。３時間後のテドラーバッグ内のトリメチルアミンガス濃度をＦＩＤ付きガスクロマトグラフにて測定し、反応前後のトリメチルアミンガスの濃度変化からトリメチルアミン除去量［ｍｇ］を求め、これを試料の重量で割ることにより、除去容量［ｍｇ／ｇ］を算出した。
(Method for measuring trimethylamine removal performance)
A 5 L Tedlar bag was filled with 25 mg of air containing 100 ppm of trimethylamine gas, 50 RH% air, and 30 mg of an organic compound adsorption removing agent. The Tedlar bag was shaken as appropriate so that the organic compound adsorption / removal agent contained therein and the air containing trimethylamine sufficiently contacted and reacted. The ambient temperature around the Tedlar bag was 25 ° C. The trimethylamine gas concentration in the Tedlar bag after 3 hours was measured with a gas chromatograph with FID, and the trimethylamine removal amount [mg] was determined from the change in the trimethylamine gas concentration before and after the reaction, and this was divided by the weight of the sample to remove the volume. [Mg / g] was calculated.
（実施例１）
塩化第２鉄六水和物（ナカライテスク社製）１３．５ｇを６０ｍｌのイオン交換水に溶解させ、３０％過酸化水素水（ナカライテスク社製）５．０ｇ添加した後、１５分間撹拌した。その後、炭酸アンモニウム（ナカライテスク社製）１２．０ｇを含有する水溶液１００ｍｌをゆっくりと添加した。添加後、１時間撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、１２０℃、窒素気流下で一昼夜乾燥したところ、赤褐色の鉄化合物粒子Ａが得られた。得られた鉄化合物粒子ＡのＢＥＴ比表面積は２１２ｍ2／ｇであった。
硝酸銀（ナカライテスク社製）２３．０ｍｇを６０ｍｌのイオン交換水に溶解させ、上記で得られた鉄化合物粒子Ａ３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液５４２ｍｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、０．５重量％銀化合物を担持した鉄化合物粒子を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
Example 1
13.5 g of ferric chloride hexahydrate (manufactured by Nacalai Tesque) was dissolved in 60 ml of ion-exchanged water, 5.0 g of 30% hydrogen peroxide (manufactured by Nacalai Tesque) was added, and the mixture was stirred for 15 minutes. . Thereafter, 100 ml of an aqueous solution containing 12.0 g of ammonium carbonate (manufactured by Nacalai Tesque) was slowly added. After the addition, the mixture was stirred for 1 hour. The obtained solution was filtered, washed with ion exchange water until the filtrate became neutral, and then dried at 120 ° C. under a nitrogen stream for 24 hours to obtain reddish brown iron compound particles A. The obtained iron compound particles A had a BET specific surface area of 212 m 2 / g.
23.0 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 60 ml of ion-exchanged water, and 3.0 g of the iron compound particles A obtained above were added and stirred well. Further, 542 mg of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried for 60 days at 60 ° C. under a nitrogen stream. As a result, iron compound particles carrying 0.5% by weight of silver compound were obtained. The organic compound removing agent contained was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
（実施例２）
硝酸銀（ナカライテスク社製）２３１ｍｇを１２０ｍｌのイオン交換水に溶解させ、実施例１で得られた鉄化合物粒子Ａ３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液５．０ｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、５重量％銀化合物を担持した鉄化合物粒子を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Example 2)
231 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 120 ml of ion-exchanged water, and 3.0 g of the iron compound particles A obtained in Example 1 were added and stirred well. Further, 5.0 g of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for a whole day and night, containing iron compound particles carrying 5% by weight of a silver compound. An organic compound remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
（実施例３）
硝酸銀（ナカライテスク社製）１．８８ｇを３００ｍｌのイオン交換水に溶解させ、実施例１で得られた鉄化合物粒子Ａ３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液３０ｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、３０重量％銀化合物を担持した鉄化合物粒子を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Example 3)
1.88 g of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 300 ml of ion exchange water, and 3.0 g of the iron compound particles A obtained in Example 1 were added and stirred well. Further, 30 g of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion-exchanged water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for a whole day and night, containing iron compound particles carrying 30% by weight of a silver compound. An organic compound remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
（実施例４）
硫酸第２鉄ｎ水和物（ナカライテスク社製）１４．３ｇを１００ｍｌの水に溶解させ、炭酸水素ナトリウム（ナカライテスク社製）６．４ｇを含有する水溶液１００ｍｌをゆっくりと添加した。添加後、１時間撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、１２０℃、窒素気流下で一昼夜乾燥した後、空気下３００℃条件で３時間焼成処理を施した。黒褐色の鉄化合物粒子Ｂが得られた。得られた鉄化合物粒子ＢのＢＥＴ比表面積は７２ｍ2／ｇであった。
硝酸銀（ナカライテスク社製）２３１ｍｇを１２０ｍｌのイオン交換水に溶解させ、上記で得られた鉄化合物粒子Ｂ３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液５．０ｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、５重量％銀化合物を担持した鉄化合物粒子を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
Example 4
14.3 g of ferric sulfate n-hydrate (Nacalai Tesque) was dissolved in 100 ml of water, and 100 ml of an aqueous solution containing 6.4 g of sodium hydrogen carbonate (Nacalai Tesque) was slowly added. After the addition, the mixture was stirred for 1 hour. The obtained solution was filtered off, washed with ion-exchanged water until the filtrate became neutral, dried at 120 ° C. under a nitrogen stream for a whole day and night, and then subjected to a calcination treatment under air at 300 ° C. for 3 hours. Black-brown iron compound particles B were obtained. The obtained iron compound particles B had a BET specific surface area of 72 m 2 / g.
231 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 120 ml of ion-exchanged water, and 3.0 g of the iron compound particles B obtained above were added and stirred well. Further, 5.0 g of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for a whole day and night, containing iron compound particles carrying 5% by weight of a silver compound. An organic compound remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
（比較例１）
硝酸銀（ナカライテスク社製）２．３ｍｇを１２０ｍｌのイオン交換水に溶解させ、実施例１で得られた鉄化合物粒子Ａ３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液５４．２ｍｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、０．０５重量％銀化合物を担持した鉄化合物粒子を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Comparative Example 1)
2.3 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 120 ml of ion-exchanged water, and 3.0 g of the iron compound particles A obtained in Example 1 were added and stirred well. Further, 54.2 mg of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for a whole day and night. As a result, iron compound particles carrying 0.05% by weight of a silver compound were obtained. The organic compound removing agent contained was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
（比較例２）
硝酸銀（ナカライテスク社製）６．６０ｇを５００ｍｌのイオン交換水に溶解させ、実施例１で得られた鉄化合物粒子Ａ３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液１００ｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、６０重量％銀化合物を担持した鉄化合物粒子を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Comparative Example 2)
6.60 g of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 500 ml of ion exchange water, and 3.0 g of the iron compound particles A obtained in Example 1 were added and stirred well. Further, 100 g of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for 24 hours to contain iron compound particles carrying 60% by weight of a silver compound. An organic compound remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
（比較例３）
硝酸銀（ナカライテスク社製）２３１ｍｇを１２０ｍｌのイオン交換水に溶解させ、α−ＦｅＯＯＨ（戸田工業製ゲータイト、ＢＥＴ比表面積１９ｍ2／ｇ）３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液５．０ｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、５重量％銀化合物を担持した鉄化合物粒子を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Comparative Example 3)
231 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 120 ml of ion exchange water, and 3.0 g of α-FeOOH (Toda Kogyo Goethite, BET specific surface area of 19 m 2 / g) was added and stirred well. Further, 5.0 g of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for a whole day and night, containing iron compound particles carrying 5% by weight of a silver compound. An organic compound remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
実施例１〜４、比較例１〜３の有機化合物吸着除去剤に関して、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した結果を表１に示す。表１より明らかなように、本発明である実施例１〜３は、銀化合物の担持量が少ない場合（比較例１）、および、銀化合物の担持量が多い場合（比較例２）と比較して高除去性能であることが分かる。また、鉄化合物のＢＥＴ比表面積が小さい場合（比較例３）も本発明である実施例２、および、４と比較して性能が低いことが分かる。 Table 1 shows the results of measuring the formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance of the organic compound adsorption / removal agents of Examples 1 to 4 and Comparative Examples 1 to 3. As is clear from Table 1, Examples 1 to 3 according to the present invention are compared with the case where the supported amount of the silver compound is small (Comparative Example 1) and the case where the supported amount of the silver compound is large (Comparative Example 2). It can be seen that the removal performance is high. It can also be seen that when the iron compound has a small BET specific surface area (Comparative Example 3), the performance is low compared to Examples 2 and 4 of the present invention.
（比較例４）
硝酸銀（ナカライテスク社製）２３１ｍｇを１２０ｍｌのイオン交換水に溶解させ、ＮａＹゼオライト（Ｎａイオンを対イオンとするＹ型ゼオライト、ＢＥＴ比表面積８２５ｍ2／ｇ）３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液５．０ｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、５重量％銀化合物を担持したＮａＹゼオライトを含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Comparative Example 4)
231 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 120 ml of ion-exchanged water, and 3.0 g of NaY zeolite (Y-type zeolite having Na ion as counter ion, BET specific surface area of 825 m 2 / g) was added and stirred well. . Further, 5.0 g of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for 24 hours. When the organic solution contained NaY zeolite supporting 5 wt% silver compound, A compound remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
（比較例５）
硝酸銀（ナカライテスク社製）２３１ｍｇを１２０ｍｌのイオン交換水に溶解させ、１３Ｘゼオライト（ＢＥＴ比表面積６８７ｍ2／ｇ）３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液５．０ｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、５重量％銀化合物を担持した１３Ｘゼオライトを含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Comparative Example 5)
231 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 120 ml of ion-exchanged water, and 3.0 g of 13X zeolite (BET specific surface area 687 m 2 / g) was added and stirred well. Further, 5.0 g of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion-exchanged water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for a whole day and night. An organic containing 13X zeolite supporting 5 wt% silver compound was obtained. A compound remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
（比較例６）
硝酸銀（ナカライテスク社製）２３１ｍｇを１２０ｍｌのイオン交換水に溶解させ、粉末状活性炭（木質系、ＢＥＴ比表面積１１１０ｍ2／ｇ）３．０ｇを添加し、よく撹拌した。さらに、２％水酸化ナトリウム水溶液５．０ｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、５重量％銀化合物を担持した活性炭を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Comparative Example 6)
231 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 120 ml of ion-exchanged water, and 3.0 g of powdered activated carbon (woody system, BET specific surface area of 1110 m 2 / g) was added and stirred well. Further, 5.0 g of 2% aqueous sodium hydroxide solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, then dried at 60 ° C. under a nitrogen stream for one day, and then an organic compound containing activated carbon carrying a 5 wt% silver compound. A remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
実施例２、比較例４〜６の有機化合物吸着除去剤に関して、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した結果を表２に示す。表２より明らかなように、本発明である実施例２は、担持体がＮａＹゼオライトである場合（比較例４）、担持体が１３Ｘゼオライトである場合（比較例５）、および、担持体が活性炭である場合（比較例６）と比較して高除去性能であることが分かる。 Table 2 shows the results of measurement of formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance for the organic compound adsorption / removal agents of Example 2 and Comparative Examples 4 to 6. As is clear from Table 2, Example 2 according to the present invention includes a case where the support is NaY zeolite (Comparative Example 4), a case where the support is 13X zeolite (Comparative Example 5), and a case where the support is It turns out that it is high removal performance compared with the case where it is activated carbon (comparative example 6).
（比較例７）
硝酸銀（ナカライテスク社製）２３１ｍｇを１２０ｍｌのイオン交換水に溶解させ、実施例１で得られた鉄化合物粒子Ａ３．０ｇを添加し、よく撹拌した。さらに、水素化ホウ素ナトリウム３００ｍｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、５重量％の金属銀を担持した鉄化合物粒子を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Comparative Example 7)
231 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 120 ml of ion-exchanged water, and 3.0 g of the iron compound particles A obtained in Example 1 were added and stirred well. Further, 300 mg of sodium borohydride was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for a whole day and night, containing iron compound particles supporting 5% by weight of metallic silver. An organic compound remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
（比較例８）
硝酸銀（ナカライテスク社製）２３１ｍｇを１２０ｍｌのイオン交換水に溶解させ、実施例１で得られた鉄化合物粒子Ａ３．０ｇを添加し、よく撹拌した。さらに、２％塩化ナトリウム水溶液５．０ｇをゆっくりと添加し、終夜撹拌した。得られた溶液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、６０℃、窒素気流下で一昼夜乾燥したところ、５重量％の塩化銀を担持した鉄化合物粒子を含有する有機化合物除去剤が得られた。得られた有機化合物除去剤について、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した。
(Comparative Example 8)
231 mg of silver nitrate (manufactured by Nacalai Tesque) was dissolved in 120 ml of ion-exchanged water, and 3.0 g of the iron compound particles A obtained in Example 1 were added and stirred well. Further, 5.0 g of 2% sodium chloride aqueous solution was slowly added and stirred overnight. The obtained solution was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried at 60 ° C. under a nitrogen stream for a whole day and night, containing iron compound particles supporting 5% by weight of silver chloride. An organic compound remover was obtained. About the obtained organic compound removal agent, formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance were measured.
実施例２、比較例７、８の有機化合物吸着除去剤に関して、ホルムアルデヒド除去性能、酢酸除去性能、トリメチルアミン除去性能を測定した結果を表３に示す。表３より明らかなように、本発明である実施例２は、銀化合物が金属銀である場合（比較例７）、および、銀化合物が塩化銀である場合（比較例８）と比較して高除去性能であることが分かる。 Table 3 shows the results of measurement of formaldehyde removal performance, acetic acid removal performance, and trimethylamine removal performance for the organic compound adsorption / removal agents of Example 2 and Comparative Examples 7 and 8. As is apparent from Table 3, Example 2, which is the present invention, is compared with the case where the silver compound is metallic silver (Comparative Example 7) and the case where the silver compound is silver chloride (Comparative Example 8). It can be seen that the removal performance is high.
本発明の有機化合物吸着除去剤によれば、アルデヒド類、カルボン酸類、アミン類の吸着性能を長期間、常温で維持することができ、一般家庭用品等幅広い用途分野に利用することができ、産業界に寄与すること大である。 According to the organic compound adsorption remover of the present invention, the adsorption performance of aldehydes, carboxylic acids, and amines can be maintained at room temperature for a long time, and can be used in a wide range of application fields such as general household goods. It is great to contribute to the world.
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